Biomimetic design for zinc-based energy storage devices: principles, challenges and opportunities

Jian Song^a, Qian Zhang*^a, Guangjie Yang^a, Kai Qi^b, Xue Li*^c, Zhenlu Liu^a, Haoqi Yang *^d, Ho Seok Park^e, Shaohua Jiang^a, Jingquan Han^a, Shuijian He *^a and Bao Yu Xia *^be
aCo-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing 210037, China. E-mail: zhangqian5689@njfu.edu.cn; shuijianhe@njfu.edu.cn
^bKey Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, State Key Laboratory of Materials Processing and Die & Mould Technology, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology (HUST), 1037 Luoyu Rd, Wuhan 430074, China. E-mail: byxia@hust.edu.cn
^cNational and Local Joint Engineering Laboratory for Lithium-Ion Batteries and Materials Fabrication Technology, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan, China. E-mail: lixue@kust.edu.cn
^dInstitute of Technology for Carbon Neutralization, College of Electrical, Energy and Power Engineering, Yangzhou University, Yangzhou, Jiangsu 225127, China. E-mail: yanghq@yzu.edu.cn
^eCenter for Next-Generation Energy Materials and School of Chemical Engineering, Sungkyunkwan University (SKKU), 2066, Seobu-ro, Jangan-gu, Suwon, Gyeonggi-do 16419, Republic of Korea

First published on 5th August 2025

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Haoqi Yang

Haoqi Yang received his PhD in 2021 from the Key Laboratory of Bionic Engineering, Ministry of Education, Jilin University. Since 2024, he has been a faculty member at Yangzhou University. His research interests focus on biomimetic materials and manufacturing, advanced energy storage systems, and flexible wearable devices.

Shuijian He

Shuijian He is currently a full professor at the College of Materials Science and Engineering, Nanjing Forestry University, China. He received his PhD from the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, in 2016. Subsequently, he worked as a Postdoctoral Research Fellow at Utah State University in the USA and the University of Western Ontario in Canada. His research interests focus on the controllable synthesis of advanced nanomaterials and their applications in electrochemical energy storage devices, electrocatalysis reactions and environmental remediation.

Bao Yu Xia

Bao Yu Xia is currently a full professor at the School of Chemistry and Chemical Engineering at the Huazhong University of Science and Technology (HUST), China. He received his PhD degree in Materials Science and Engineering at Shanghai Jiao Tong University (SJTU) in 2010. He worked at Nanyang Technological University (NTU) from 2011 to 2016. His research interests are in energy chemistry and materials science.

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With the rapid advancement of the global economy and society, challenges such as energy scarcity and environmental pollution have become increasingly prominent.^1–4 Addressing these issues necessitates the development of renewable and clean energy sources to replace traditional fossil fuels, thereby suggesting green and efficient sustainable development strategies.^5–7 Common clean energy sources include solar, wind, geothermal, and nuclear energy sources.^8,9 However, the reliability of these clean energy sources is constrained by environmental variability, making it difficult to ensure a stable energy supply.^10,11 Additionally, nuclear energy faces significant environmental and safety concerns, limiting its large-scale adoption. To overcome these limitations, the focus must shift towards advanced energy storage systems capable of providing a continuous and reliable supply of clean energy. Developing innovative energy storage devices is essential for bridging the gap between intermittent clean energy generation and the growing demand for consistent, sustainable energy.

Up to now, lithium-ion batteries (LIBs) have achieved large-scale industrialization due to their high energy density and long cycling life and the absence of memory effect.^12,13 However, the growing societal demand for energy storage, coupled with the limitations of LIBs, such as uneven lithium resource distribution, safety concerns, and high manufacturing costs, has created a pressing need for alternative solutions.^14–16 Zinc-based energy storage (ZES) devices present a promising solution, utilizing abundant, cost-effective, and environmentally friendly zinc (Zn) metal as the anode and aqueous electrolytes as ionic conductive media.^17–19 ZES devices are inherently safe and offer diverse configurations, including zinc ion batteries (ZIBs),²⁰ zinc–air batteries (ZABs),²¹ and zinc ion capacitors (ZICs),^22,23 making them highly adaptable for various applications. Therefore, ZES device technology is gradually becoming one of the important alternative technologies to LIBs.

Compared with LIBs, ZES devices are rich in material sources, and because of the use of aqueous electrolytes,²⁴ the risk of fire and explosion caused by thermal runaway of traditional LIBs is effectively avoided.²⁵ Additionally, the preparation processes of Zn-based batteries are simpler and more cost-effective than LIBs, which is crucial for reducing the overall expense of energy storage systems. In particular, ZIBs employ Zn metal anodes and Zn²⁺ charge carriers in aqueous Zn salt electrolytes,^26,27 making them suitable for grid-level storage and portable electronics.²⁸ Rechargeable ZABs, utilizing Zn metal anodes and air cathodes, achieve high energy density by harnessing ambient oxygen gas (O₂), offering promise for electric vehicles and emergency back-up power systems.^29,30 ZICs integrate capacitive and pseudocapacitive storage mechanisms with Zn anodes and high specific-surface-area cathodes, delivering high power density and exceptional cycling stability, ideal for fast-charging and short-term energy storage applications.^31,32 With ongoing advancements in electrode materials, electrolytes, and battery structures, ZES technologies are poised to play a pivotal role in future energy systems, particularly in the domains of stationary storage, wearable electronics, and electric mobility, contributing to the realization of a sustainable, low-carbon energy landscape.

Despite their promising attributes, ZES devices face several critical challenges that hinder their practical deployment, particularly as demands for higher energy density and broader applications continue to rise. First, poor structural stability of electrode materials remains a key limitation; repeated Zn²⁺ insertion/extraction induces significant volume changes, leading to mechanical degradation processes such as pulverization and delamination, which severely compromise electrochemical performance. Second, the cycle life of ZES systems is often limited by the intrinsic instability and capacity fading of electrode materials. Third, their relatively low energy density, especially when compared to industrialized LIBs, restricts their applicability in energy-intensive scenarios. In addition, the formation of Zn dendrites during repeated charge/discharge cycling poses significant safety and durability concerns. These dendritic structures can penetrate the separator, causing internal short circuits and performance failure. Moreover, while Zn itself is abundant and inexpensive, the overall manufacturing cost of ZES devices remains high due to the reliance on high-performance materials, intricate fabrication processes and specialized equipment. Finally, the corrosive nature of commonly used aqueous electrolytes, such as zinc sulfate (ZnSO₄) or Zn(CF₃SO₃)₂, leads to anode degradation and further impairs long-term stability.^38–43

Therefore, the rational design of electrode materials with high stability and low cost, along with the optimization of electrolytes and separators, is essential to enhancing the electrochemical performance of ZES devices. However, most research efforts tend to focus on improving individual material properties, often overlooking the synergistic interactions between components. Adopting a holistic perspective, a promising approach is to draw inspiration from nature, leveraging its intricate designs and efficient structures for material innovation. This concept, widely known as “biomimetics”, offers a valuable framework for advancing the development of ZES technologies by integrating natural structures into material and device design.^44–46

Biomimetics is an interdisciplinary field that explores and mimics the structures, functions, and mechanisms of biological organisms to design and develop advanced materials, devices and systems.⁴⁷ Its core principle lies in utilizing the exceptional structures and strategies honed through billions of years of natural evolution to inspire human technological innovation. Recently, biomimetics has found a broad range of applications across materials science, engineering, medicine, architecture, and other fields.⁴⁸ Historically, the concept of biomimetics can be traced back to early human technological advancements inspired by nature. For instance, ancient Chinese craftsman Lu Ban invented the saw by observing the structure of cicada wings and Leonardo da Vinci designed flying machines based on the study of bird flight. As a systematic scientific discipline, biomimetics was formally established in the mid-20th century, with the American scientist Otto Schmitt coining the term in the 1950s.^49,50 Since then, biomimetics has gained significant traction in the interdisciplinary field of research, especially in the field of ZES devices (Fig. 1). Notable advancements include the application of a cage-like biomimetic structure in Zn–bromine batteries (ZBBs) reported in 2017, which significantly enhanced stability and cycle life,³³ and a leaf-inspired design reported in 2018 that improved electrode conductivity and electrochemical performance in ZABs.⁵¹ In 2022, an enamel-like anode protective layer was developed, enabling dendrite-free growth in ZIBs.³⁵ In 2023, a sponge-like structure was introduced, boosting both the energy storage capacity and mechanical stability of Zn–CO₂ batteries (ZCBs).³⁶ More recently, in 2024, a hierarchical root-like structure was applied to zinc–iodine (Zn–I₂) batteries, ensuring stable interfacial reactions.³⁷ These biomimetic innovations have addressed critical challenges in ZES devices, offering improved electrochemical performance, durability, and energy density. By emulating natural designs, biomimetics has opened new avenues for advancing ZES technologies and overcoming existing technical bottlenecks.

By studying and understanding the unique morphologies, structures, and functions of natural organisms, battery performance can be strategically improved and optimized. Leveraging the distinctive characteristics inherent in biological systems enables the development of more efficient and environmentally friendly batteries, paving the way for rapid commercial advancement.⁵² In recent years, biomimetic designs inspired by nature have garnered significant attention in ZES devices, yielding remarkable results. This review consolidates recent progress in biomimetic strategies applied to ZES technologies, focusing on how these designs influence the performance of various systems. By examining biomimetic design approaches across electrodes, separators, and electrolytes from three perspectives –structure, function, and surface – this review highlights their positive effects on critical performance metrics, such as cycle life, capacity stability, and electrolyte compatibility. Furthermore, this review provides a detailed analysis of how bionic design in individual components enhances the overall performance of ZES devices, offering innovative insights for performance optimization in future systems (Fig. 2). By addressing gaps in existing research, this review not only presents a comprehensive perspective on the current state of biomimetic design in ZES technologies but also charts new directions for advancing their applications. This review underscores the potential of biomimetic design to drive innovation and progress in energy storage, promoting its integration into next-generation ZES systems.

1. Biomimetic design principles

Biomimetic science, inspired by the intricate designs and functions of natural systems, represents an innovative approach to solving engineering and scientific challenges. Over billions of years of evolution, nature has developed highly efficient structures and mechanisms, such as the layered architecture of mussel shells,⁵³ the remarkable strength and flexibility of spider silk,⁵⁴ and the hierarchical porosity of bones.⁵⁵ These natural phenomena provide a wealth of inspiration for researchers. The study of biomimetic design not only drives the development of advanced materials with exceptional properties but also fosters interdisciplinary collaboration of materials science, biology, and engineering. Functional materials with bionic structural design hold significant promise for applications in aerospace,⁵⁶ medical devices,⁵⁷ energy storage,^15,58 and environmental protection.⁵⁹

To date, research on biomimetic design principles has primarily focused on three key aspects: selection of bionic raw materials, construction of bionic structures, and optimization of material properties. The selection of bionic raw materials is fundamental and involves identifying materials with properties analogous to those found in nature, such as high strength, flexibility, conductivity, or environmental resilience.^57,60,61 The construction of bionic structures aims to replicate the hierarchical organization and intricate designs observed in natural systems, utilizing advanced fabrication techniques such as three-dimensional (3D) printing,⁶² self-assembly, and nanomanufacturing to achieve precision and scalability.⁶³ Finally, the optimization of material properties is essential for improving mechanical, thermal, and functional performance, often through innovative engineering strategies and the integration of nanomaterials. The subsequent sections will provide an in-depth discussion of these three aspects, highlighting recent progress and future perspectives in the development of bionic structural materials.

1.1 Selection of bionic raw materials

Common bionic raw materials can be categorized into three main groups based on their properties: inorganic materials, organic materials, and composites. Among them, inorganic materials, including graphite,⁶⁴ carbon nanotubes (CNTs),⁶⁵ MXenes⁶⁶ and metal oxides,⁶⁷ are widely favored for their high mechanical strength, excellent electrical conductivity, and exceptional environmental adaptability. For example, Zou et al.⁶⁸ introduced coordination interactions between polyvinylpyrrolidone (PVP) and metal ions to achieve uniform metal dispersion within carbon precursors. The spatial confinement effect of PVP enabled precise control of metal–organic framework (MOF) particle size, leading to the successful fabrication of cobalt (Co) and nitrogen (N) co-doped honeycomb-like porous carbon materials (LIC-ZIF-67-M10) using a laser-induced carbonization (LIC) strategy under ambient conditions (Fig. 3a). The bionic morphology of this material, featuring a high specific surface area and open channel structure, enabled its application as an air electrode in ZABs, demonstrating outstanding cycling stability and high specific capacity.

Inspired by the Fibonacci pattern structure observed in rose, Li et al.⁶⁹ proposed a multi-scale design strategy involving crystal, atomic, and structural engineering to construct rose-like D-VS₂. This architecture featured high spatial utilization and enhanced structural stability (Fig. 3b). The integration of abundant vanadium (V) intercalation sites and sulfur (S) vacancies effectively lowered Zn²⁺ migration energy barriers and improved the overall electrochemical kinetics. Similarly, Zhang et al.⁷⁰ employed Fe-ZIF precursors and high-temperature carbonization to synthesize a 3D flower-like Fe–N–CNT structure. The hierarchical porosity and open architecture provided a large number of electrochemically active sites and enhanced the catalytic performance through rapid mass transport. Flower-inspired morphologies have emerged as a prominent motif in biomimetic materials design, rooted in the hierarchical growth and radial symmetry characteristic of natural petal arrangements. This evolutionarily optimized geometry offers several advantageous attributes, including mechanical stability, multiscale diffusion pathways, and a high surface-to-volume ratio. Compared to honeycomb-like structures, which emphasize geometric regularity and channel alignment, flower-like architectures exhibit smoother curvature transitions and a higher density of edge and corner defects—features that can significantly increase the density of active sites and promote both charge transport and ion diffusion. In contrast to root-like designs, which are often optimized for unidirectional transport and mechanical flexibility, flower-like structures exhibit superior spatial order and packing density, rendering them particularly well-suited for constructing high-loading composite electrodes and complex multiphase interfaces.

Within the framework of ZIBs, flower-inspired architectures offer distinct advantages for the multiscale regulation of cathode materials. The 3D radial configuration not only accommodates volumetric fluctuations during cycling but also improves electrolyte infiltration, thereby enhancing electrode–electrolyte contact. Moreover, the centrosymmetric morphology inherently promotes the establishment of multidirectional and continuous electron/ion transport pathways from the interior to the exterior, contributing to superior rate capability. Beyond their high specific surface area, such structures also exhibit enhanced mechanical stability and facilitate synergistic electrochemical interactions, positioning them as a promising platform for achieving both structural integrity and high-performance energy storage.

MXenes, a novel family of two-dimensional (2D) materials, have also been extensively explored in biomimetic material design due to their layered morphology and surface tunability. Li et al.⁷¹ developed an accordion-like VO_x/Mn–V₂C composite formed via manganese ions (Mn²⁺) pre-intercalation followed by in situ electrochemical oxidation. The unique accordion-like structure significantly improved the electrochemical performance, with the fabricated electrodes exhibiting excellent cycling stability when used in ZABs.

Organic materials offer advantages such as processability, film-forming ability, flexibility, and abundant hydrophilic functional groups, which contribute to their unique morphologies, excellent mechanical properties, and biocompatibility.⁷² These characteristics make them particularly suitable for fabricating bionics electrolytes and separators in battery systems. For example, Yang et al.⁷³ employed deep eutectic solvents (DES) to regulate the nanoscale phase separation (<1 μm) in ultrahigh-molecular-weight polyethylene oxide (UHMPEO) and polyvinylidene fluoride (PVDF) blends, successfully developing neuron-inspired polymer electrolytes (Neu-PE) (Fig. 3c). During ion transport, lithium ions (Li⁺) preferentially coordinate with ether oxygen atoms in UHMPEO, forming Li⁺⋯C–O–C interactions, which disrupt the excessive formation of PEO–Li⁺–PVDF complexes. This selective coordination leads to a hierarchical architecture reminiscent of biological joint tissues (bone-_PVDF/leanDES, articular cartilage-_{UHMPEO/PVDF/DES}, and synovial fluid-_UHMPEO/DES). These electrolytes exhibited exceptional toughness and puncture resistance, while the incorporation of DES significantly enhanced their non-flammability. The resulting Neu-PE demonstrated superior performance in half-cell applications compared to conventional electrolytes. Additionally, inspired by the structure of fish nets, Liu et al.⁷⁴ synthesized high-strength, ultra-flexible electrolytes through a nucleophilic addition rection between the –NCO group in 2-isocyanatoethyl methacrylate and the –OH group in N²,N⁶-bis(2-hydroxyethyl)pyridine-2,6-dicarboxamide (Fig. 3d). The fishnet-like polyzwitterion skeleton synergistically regulated the transport of Li⁺ and anions, enabling dendrite-free operation in solid-state batteries.

Some organic materials exhibit good conductivity and can function as electrode materials. However, the limited conductivity and uncontrollable morphology of most organic materials restrict their practical applications. To overcome these limitations, combining inorganic and organic materials has emerged as an effective strategy to develop high-strength, lightweight, and multifunctional biomimetic materials. For instance, inspired by the amphiphilicity of cell membranes, Luogu et al.⁷⁵ fabricated a PEDOT@MnO₂@carbon cloth (PMC) composite electrode by electrodepositing a poly(3,4-ethylenedioxythiophene) (PEDOT) layer with excellent electrochemical stability and hydrophobicity onto a hydrophilic α-MnO₂/carbon-based electrode (Fig. 3e). The PEDOT layer effectively enhances the overall conductivity of the electrode, reduces the desolvation energy barrier of hydrated Mg²⁺, and suppresses cathode dissolution. When applied in aqueous magnesium–ion batteries, the PMC electrode exhibits outstanding rate performance (58.4 mAh g⁻¹ at 3 A g⁻¹) and cycling stability (85.92 mAh g⁻¹ after 1000 cycles at 2 A g⁻¹). Similarly, Xiao et al.⁷⁶ fabricated erythrocyte-like composite materials (CuS@PANI) by in situ polymerizing polyaniline (PANI) onto CuS surfaces through a simple solvothermal method (Fig. 3f). The PANI layer effectively mitigated the pulverization of CuS, while the NH⁺ groups on the surface were bound with anions, contributing to batteries with an outstanding cycle life of up to 7500 cycles.

1.2 Construction of bionic structures

Insights drawn from the structural and functional complexity of plants, animals, and humans have inspired the design of advanced materials with superior properties compared to conventional systems.^61,77,78 The construction of bionic structures can be categorized into three main approaches: structural bionics, functional bionics, surface and interfacial bionics. Structural bionics involves mimicking the microscopic and macroscopic structures of organisms to achieve excellent characteristics such as high strength, durability, and lightness. For instance, coiled structures in nature, such as those found in vines and the spiral tendrils, have garnered significant attention due to their strong mechanical and tensile properties and excellent shape adaptability.^79,80 Based on this, Lee et al.⁸¹ developed a deoxyribonucleic acid (DNA)-like supercoiled architecture using spandex fiber as a stretchable core, helically wrapped with multi-walled carbon nanotubes (MWCNTs) serving as a conductive sheath, and embedded with Zn (40–60 nm) and manganese dioxide (MnO₂, >10 μm) particles (Fig. 4a). This structure was fabricated via a continuous over-twist insertion process, resulting in a mechanically stable electrode with enhanced ion transport channels established through physical anchoring of the active particles within the MWCNT matrix. The supercoiled design enabled the Zn/MnO₂ electrode to exhibit remarkable tensile capacity (800%), high linear capacity (0.029 mAh cm⁻¹), minimal initial length (29%), outperforming conventional non-coil (200%) and standard coil (500%) structures. Electrochemical characterization confirmed superior stability and durability, marking a notable advancement in the development of stretchable energy devices.

In addition to mechanical adaptability, the subtle structural designs found in nature continue to inspire technological innovation across disciplines. Inspired by the aerodynamic properties of tristellateia seeds, Kim et al.⁸² developed bioinspired 3D micro-, meso-, and macro-fliers with hierarchical architectures through the integration of full-scale computational modeling, multiscale fabrication techniques and micromachining technology (Fig. 4b). By analyzing, calculating, and testing the structural aerodynamics of 3D structures across micro-, meso-, and macro-scales, they achieved precise replication of the natural seed autorotational descent mechanism and optimized the composition and hierarchical architecture to achieve enhanced rotational dynamics and ultralow terminal velocity. This research establishes a foundation for large-scale spatial systems such as environmental monitoring, population census, and other spatially distributed applications. Furthermore, Niu et al.⁸³ prepared a bifunctional catalyst featuring a Co/CoFe heterostructure dispersed within a 3D flower-like graphite carbon matrix via a coordination construction-cation exchange-pyrolysis strategy. The synergistic interaction between the metal heterostructure and the flower-like support enhanced conductivity and reaction kinetics, addressing issues such as low energy conversion efficiency and limited cycling capacity in air cathodes. The electrode demonstrated excellent activity for both oxygen evolution reactions (OERs) and oxygen reduction reactions (ORRs).

Structural bionics enhances the electrochemical performance of materials by mimicking the morphologies of natural species, effectively addressing macroscopic design challenges in electrode systems. However, its ability to regulate microscopic functionalities remains limited. To overcome these limitations, functional bionics has emerged, focusing on replicating specific biological functions found in nature,⁸⁴ such as nutrient transport channels in wood⁸⁵ or cell membrane structures.⁸⁶ For example, Liu et al.,⁸⁷ inspired by the functional distribution in crocodile skin, where thick, rigid osteoderms overlay a thin, flexible dermis, designed flexible battery devices integrated into energy storage and deformation zones (Fig. 4c). This rigid-flexible integration enabled the devices to accommodate complex deformations, such as multi-directional winding, folding, and stretching. The fabricated rigid-flexible integrated LIBs retained 92.3% of their capacity after 30000 bends and 200 cycles. Finite element analysis (FEA) showed that the flexible parts absorbed most of the stress during bending, with stress values of 2.2 MPa and 54.9 MPa at 157.5° bending for rows and columns, respectively. In another study, Yin et al.⁸⁸ mimicked the self-protective gum secretion mechanism in peach trees to enhance the stability of solid-state electrolytes. Inspired by the formation of a sealing barrier at damage sites, they engineered a cathode electrolyte interphase (CEI) layer by selecting LiBH₄–Se and LiBH₄–S systems with low bond dissociation energies (Fig. 4d). This design yielded a robust CEI after 30 cycles, significantly improving ion conductivity and electrochemical performance. Similarly, Li et al.⁸⁹ utilized sodium hyaluronate (SH), a component of the human extracellular matrix known for its water-retention, lubrication, and tissue-repair properties, to stabilize Zn anodes in aqueous systems. The hydrophilic and Zn-affinitive functional groups in SH effectively suppressed dendrite formation, resulting in batteries with outstanding cycling stability and reversibility.

Surface and interfacial bionics focuses on mimicking the properties and functions of biological surface structures in nature to enhance performance.⁹² For example, bacterial cellulose (BC) has attracted considerable attention due to its unique structure, high water absorption and retention, permeability to liquids and gases, and exceptional wet strength.⁹³ Inspired by the outstanding hydrophilicity of BC, Qiu et al.⁹⁰ utilized its hydrogen-bonding self-assembly properties in combination with nano-hydroxyapatite (HAP, Ca₂(PO₄)₆(OH)₂) particles derived from animal bone to fabricate a high-performance separator (ZnHAP/BC) (Fig. 4e). This design synergistically regulated electrolyte dissolution and ion transport kinetics, effectively suppressing interfacial side reactions. The resulting separator exhibited excellent toughness, mechanical strength, and ion dynamics, contributing to the assembled battery's superior electrochemical performance. Zhang et al.⁹¹ drew inspiration from drug slow-release mechanisms, which mimic cell membranes, to develop an indium-chelated resin protective layer (Chelex-In) on the Zn anode surface (Fig. 4f). The Chelex-In layer provided a continuous slow release of indium, enabling persistent heterogeneous nucleation sites for Zn²⁺ and reducing hydrogen evolution reactions (HER). Molecular dynamics (MD) simulations indicated that the selective permeability of Chelex-In effectively blocked vanadate ions and further inhibited Zn dendrite growth. Using V₂O₅ as the counter electrode, the system achieved a remarkable cycle life of 2800 hours with a coulombic efficiency (CE) of 99.85%, demonstrating excellent cycling stability.

1.3 Optimization of material properties

Optimizing material composition is a critical factor in enhancing the performance of bionic materials. By fine-tuning the composition, significant improvements in mechanical properties, tensile strength, and chemical stability can be achieved, facilitating the development of high-performance materials.⁹⁴ Taking the innovation of bio-based materials as an example, Mi et al.⁹⁵ utilized CRISPR-Cas9 gene-editing technology to directionally integrate spider silk protein genes into the genome of domestic silkworms, resulting in the biosynthesis of fully polyamide spider silk fibers (Fig. 5a). These fibers exhibited remarkable mechanical strength (1299 MPa) and toughness (319 MJ m⁻³), surpassing the performance limits of natural materials and significantly expanding the future application scenarios. Notably, this breakthrough in cross-species genetic recombination provides novel insights for developing bio-inorganic hybrid systems. In the realm of inorganic composites, Liu et al.⁹⁶ addressed the low conductivity challenge of sea urchin-like NiCo₂S₄ by synthesizing a bifunctional hybrid catalyst through a synergistic hydrothermal synthesis and sulfurization modification processes. The optimized material exhibited enhanced electron conductivity, improved structural stability, and catalytic activity. Crucially, dual optimization was achieved through composition gradient engineering and microstructural regulation, enabling both effective conductive network reconstruction and active site exposure. This work not only validates the effectiveness of multiscale composition control strategies, but also establishes a new paradigm for the rational development of advanced materials for energy conversion applications, highlighting the potential of composition optimization in improving material functionality and performance.

Structural optimization plays a pivotal role in enhancing the performance of bionic materials. Leveraging advanced computational simulations and manufacturing technologies enables the rational design of structures, thereby improving the energy density, lifespan, and rate performance of electrode materials. For example, the xylem in wood, composed of interconnected catheters and tracheid, efficiently transports water and inorganic salts, supporting plant growth and metabolism.⁹⁸ These structures provide abundant conductive pathways and high active surface areas, facilitating rapid transport and absorption of essential nutrients. Inspired by this natural design, Men et al.⁹⁹ used advanced 3D printing techniques to mimic xylem channel structures, developing bio-inspired multi-channel cathode (BMC) materials. These materials, optimized for conductivity and channel morphology, demonstrated exceptional O₂ transport efficiency and outstanding ORR performance when applied as cathodes in ZABs. Similarly, Chen et al.⁹⁷ employed Prussian blue analogues (PBAs) as precursors to fabricate virus-like Co–N–Cs nanomaterials with vertically aligned outer CNTs and an internal core through direct carbonization (Fig. 5b). The virus-like rough surfaces provided high specific surface areas, while N and Co dual-doping synergistically enhanced the catalytic activity. By pairing these cathodes with an ultra-stretchable alkaline electrolyte, major challenges in ZABs were effectively addressed. Further optimization of the stretchable electrolyte was demonstrated through stress–strain curve analysis (Fig. 5c1) and tolerance schematics (Fig. 5c2), ensuring excellent adaptability and performance.

In summary, the development of functional materials with bionic structures embodies a multidisciplinary research frontier at the intersection of materials science, biology, and engineering. Through systematic exploration of bionic raw material selection, structural design, and performance optimization, it is possible to engineer high-performance materials with broad applicability. Continued technological innovation, coupled with interdisciplinary collaboration, is poised to propel the field forward, unlocking transformative solutions for diverse scientific and industrial challenges. Expanding the applications of bionic materials will not only advance technological progress but also address complex problems with innovative strategies.

2. Zinc-ion batteries

In 1799, Alessandro Volta invented the first battery, the voltaic pile, using Zn metal as the anode. Since then, Zn has remained a classic anode material, leading to the successful commercialization of various Zn primary batteries, many of which are still in widespread use today.^21,100,101 Over time, advancements in Zn-based battery systems have included the replacement of alkaline electrolytes with mildly acidic ones, effectively improving charge/discharge performance and cycle life. These innovations have garnered significant attention and spurred notable progress in the field. Structurally, ZIBs are similar to LIBs, comprising cathodes, anodes, separators, and electrolytes.^102,103 In recent years, researchers have focused on modifying the structure and composition of electrode materials, separators, and electrolytes, achieving incremental improvements in ZIB performance (Fig. 6a and b). Over the course of evolution and natural selection, the structures of plants and animals, despite their apparent simplicity, have attained an extraordinary level of functional optimization. Nature has long served as a source of inspiration for revolutionary discoveries in human development. Consequently, the biomimetic modifications of material structures and functions, followed by systematic industrial advancements, hold immense potential for practical applications and transformative innovation.^103,104

2.1 Cathodes

The electrochemical performance of ZIBs is often constrained by the limitations of cathode materials. While the radius of Zn²⁺ (0.75 Å) is comparable to that of Li⁺ (0.76 Å), the aqueous electrolyte in ZIBs facilitates the formation of hydrated Zn²⁺ with a +2 charge, which leads to strong electrostatic repulsion during cycling. This presents a greater challenge compared to LIBs, sodium-ion batteries (SIBs), and potassium-ion batteries (PIBs).^105,106 Consequently, significant research efforts are focused on the development of advanced cathode materials to address these challenges.¹⁰⁷ Cathodes in ZIBs are typically categorized into three classes according to their reaction mechanism: Zn²⁺ insertion/extraction, Zn²⁺ and H⁺ co-insertion/extraction, and chemical conversion reactions.^103,108 Among these, the Zn²⁺ insertion/extraction mechanism is the most widely studied and is analogous to that of LIBs, relying on the reversible intercalation and deintercalation of Zn²⁺ within the cathode material. Common cathode materials include those with layered structures, particularly V-based and manganese (Mn)-based compounds (Fig. 6c).^109,110

Various electrode materials have been extensively explored as cathodes for ZIBs, demonstrating promising electrochemical performance. However, the straightforward design of electrode materials alone often falls short in significantly enhancing the overall performance of ZIBs. In contrast, bionic-structured materials, inspired by nature and refined through long-term evolution, exhibit superior functional regulation and performance optimization. This section reviews the application of bionic-structured materials in the development of advanced cathode materials for ZIBs.

2.2 Anodes

The design and optimization of cathodes in ZIBs play a critical role in improving their electrochemical performance. However, as an indispensable component of ZIBs, the stability of the Zn anode during cycling is equally crucial to the overall performance of the battery.¹⁴⁷ The Zn anode faces significant challenges throughout the operational lifecycle of ZIBs, including Zn dendrite growth, the HER process during charging, passivation during discharge, and corrosion (Fig. 10) during the resting period after assembly.¹⁴⁸

2.3 Separators

A separator is a critical component of batteries, serving primarily to maintain physical separation between the cathode and anode, thereby preventing short circuits and associated safety risks.^167,168 In addition, separators facilitate the selective passage of Zn²⁺ while inhibiting electron transport and exhibit excellent wettability properties.¹⁶⁹ Consequently, separator is typically designed with high ionic conductivity, robust mechanical strength, and superior chemical and thermal stability. Common materials used for separators include filter paper, hydrophilic polyolefin, and glass fibers.¹⁷⁰ With the increasing demand for energy storage systems, the performance requirements for batteries have grown correspondingly. Beyond safety considerations, advanced separators must address additional functional demands. In response, novel strategies for functionalized separators have been proposed to enhance the versatility and safety of ZIBs across diverse applications. Inspiration from biological systems, including structures like nuclear membranes, cell membranes, and endoplasmic reticulum membranes, as well as larger-scale analogues like insect wing membranes, eggshell membranes, and snake skin membranes, offers innovative approaches for designing functionalized separators. Several biomimetic designs inspired by these biological structures have been extensively explored in recent studies to optimize separator functionality.

Cell membranes play a crucial role in maintaining cellular homeostasis by facilitating efficient material and energy exchange with the external environment, leveraging their unique properties of hydrophilicity, lipophilicity, and selective permeability. Inspired by the selective permeability of the potassium channel (KcsA) in plasma membranes, Zhang et al.¹⁷¹ designed a biomimetic separator (PMCl) with excellent Zn²⁺ permeability. The design integrates a metal–organic-framework (MOF) skeleton functionalized with perchlorate groups (MOF-ClO₄) into a hydrophobic polystyrene (PS) matrix via electrospinning, yielding a well-ordered ion transport architecture with a channel diameter of ∼6.7 Å (Fig. 14a). This architecture enables preferential transport of Zn²⁺ while effectively excluding SO₄²⁻ anions, achieving a high Zn²⁺ flux of 1.9 × 10⁻³ mmol m⁻² s⁻¹ and a Zn²⁺/SO₄²⁻ selectivity ratio of ∼10. As a result, the Zn²⁺ transference number increased markedly to 0.88 for PMCl–Zn, surpassing those of bare Zn(0.64) and PS–Zn(0.69) by 37.5% and 27.5%, respectively. The separator also exhibited enhanced hydrophobicity, with the contact angle increasing from 62.6° (bare Zn) to 123.4°, effectively inhibiting water infiltration and parasitic side reactions. Electrochemical measurements further confirmed the improved interfacial stability of PMCl–Zn. The corrosion potential increased to 0.016 V, outperforming both PS–Zn (0.011 V) and bare Zn (0.009 V), reflecting superior corrosion resistance. DFT calculations revealed a binding energy of −4.47 eV for PMCl–Zn, significantly stronger than that of bare Zn (−0.93 eV), indicating enhanced interfacial affinity that promotes uniform Zn deposition and dendrite suppression. Kinetic analysis revealed a reduced desolvation activation energy of 34.9 kJ mol⁻¹ for PMCl–Zn, a 35.1% decrease compared to bare Zn (53.8 kJ mol⁻¹), along with an approximately twofold increase in exchange current density (from 3.7 to 7.2 mA cm⁻²), suggesting accelerated interfacial charge transfer. Additionally, batteries assembled with the PMCl separator exhibited remarkable capacity retention even after extensive bending. Atomic force microscopy (AFM) 3D height mapping revealed that the introduction of PMCl effectively suppressed dendrite formation and the HER, significantly extending battery cycle life. Furthermore, the protein membrane found between the embryo and eggshell in oviparous animals, which enables gas exchange while preventing water ingress, serves as an inspiring natural analogue. This evolutionary optimized structure has attracted significant attention for its exceptional functional properties.

Zhai et al.¹⁷² utilized the unique properties of eggshell membranes (ESM) by thermally denaturing the membrane proteins, thereby exposing ten times more Zn-affinity sites while maintaining the semi-permeability of the ESM (Fig. 14b). This modified structure enabled the membrane to effectively block water diffusion in the electrolyte while promoting the deposition of active Zn²⁺ due to the increased Zn-affinity sites and simultaneously repelling solvated Zn²⁺. Notably, the denatured ESM retained excellent mechanical strength, allowing it to accommodate significant volume changes during Zn deposition. Batteries assembled with this ESM-based separator demonstrated excellent electrochemical performance, including superior rate capability, a high CE of 99.8% over 500 cycles, effective suppression of side reactions, exceptional cycle stability (5000 hours), and a low energy barrier for Zn/Zn²⁺ conversion. These examples underscore the potential of bio-inspired membranes to enhance the electrochemical performance of ZIBs by emulating the functionality of natural membranes. Although only specific functions of biological membranes are replicated, the resulting improvements, such as mitigating side reactions on the Zn anode surface, represent a significant step forward. These findings highlight promising new directions for designing cost-effective, high-performance separators with industrial scalability to address the challenges faced in practical ZIB applications.

2.4 Electrolytes

The use of aqueous electrolytes is a key advantage of ZIBs; it also introduces some side reaction issues. As essential components of ZIBs, electrolytes must facilitate rapid Zn²⁺ transport while exhibiting high ionic conductivity, stability, cost-effectiveness, and environmental friendliness. Typically, aqueous ZIB electrolytes are composed of soluble Zn salts, such as ZnSO₄, Zn(OTf)₂, and Zn(TFSI)₂.¹⁷⁵ Designing bio-inspired functional electrolytes for diverse applications holds great potential to overcome existing limitations. One significant challenge for aqueous ZIBs is their poor performance under low-temperature conditions due to the freezing of electrolytes. In nature, cold-adapted organisms, including plants (e.g., fir, spruce, and tundra plants), animals (e.g., polar bears, penguins and snow hares) and microorganisms (e.g., psychrophilic bacteria, polar molds, and polar pseudomonads) exhibit remarkable cold resistance mechanisms. Inspired by these strategies, Hu et al.¹⁷⁶ introduced extracellular polysaccharides that inhibit ice crystal nucleation and growth to enhance the anti-freezing properties of electrolytes. Specifically, quaternate galactomannan polysaccharide (q-GPA) was employed as a bio-inspired additive to improve electrolyte performance at subzero temperatures. Spectroscopy and MD simulations revealed that the quaternary ammonium groups distributed along the q-GPA backbone reduced water activity, effectively suppressing ice crystal formation. Furthermore, the quaternary ammonium groups facilitated uniform electric field distribution, enabling the formation of a homogenous Zn deposition layer. Benefiting from the synergistic effect of the Zn anode interface electric field and the quaternary ammonium salt, the prepared electrolyte exhibited excellent anti-freezing properties. The assembled Zn‖Na₂V₆O₁₆·1.5H₂O battery demonstrated a remarkable cycle life of 5000 cycles at −30 °C, with a capacity retention rate of 99.2%.

Although the biomimetic strategy has shown significant potential in enhancing the low-temperature performance of aqueous electrolytes, in practical applications such as flexible wearable electronic devices, the electrolytes need to possess excellent mechanical strength, interfacial adhesion, self-repairing, and high ionic conductivity to cope with interfacial instability and performance degradation due to mechanical stresses such as bending and compression. Therefore, the construction of gel polymer electrolytes (GPE) with multi-functional integration capability has become one of the key directions of current research. Especially under the actual service conditions, there are often coupling and trade-offs between different parameters, and how to achieve the synergistic optimization of multiple parameters by bionic has become an important challenge and research hotspot in the design of electrolytes for flexible ZIBs. In response to this, Wang et al.¹⁷³ designed a multi-parameter synergistically optimized biomimetic GPE by integrating the adhesion mechanism of mussel foot proteins with hydrophobic surface engineering. Inspired by the strong adhesion of mussel peduncle filaments, dopamine (DA) containing catechol groups were grafted onto sodium alginate (SA) to yield DA–Alg, imparting an interfacial adhesion strength of 80 kPa, representing a 185.7% increase over the reference PAAm–O system (28 kPa). To emulate hydrophobic surface behavior observed in natural membranes, DA–Alg was physically crosslinked with poly(acrylamide-co-octadecyl methacrylate) (PAAm–O), forming a hydrophobically crosslinked DA–Alg/PAAm–O network (Fig. 14c). This architecture not only enhanced mechanical robustness, with a tensile strength of 382 kPa (compared to 361.7 kPa for PAAm–O and 2.4 kPa for PAAm), but also endowed the material with excellent self-healing ability, maintaining 72.4% recovery efficiency after five damage–healing cycles. The incorporation of long-chain hydrophobic groups effectively suppressed swelling (<10% volume change after 6 h in 2 M ZnSO₄), while simultaneously constructing continuous ion transport pathways. This structural synergy yielded a high ionic conductivity of 32.3 mS cm⁻¹, a 32.4% enhancement over PAAm–O. Moreover, the activation energy for Zn²⁺ transport was reduced from 26.5 to 23.3 kJ mol⁻¹, and the Zn²⁺ transference number (t_Zn²⁺) increased from 0.43 to 0.60 (a 39.5% improvement), indicating improved ion selectivity and lower energy barriers for desolvation. This dual biomimetic strategy enabled the simultaneous enhancement of interfacial adhesion, ion mobility, mechanical durability, and long-term cycling stability. The GPE exhibited 91% capacity retention after 4000 cycles at 4 A g⁻¹ and maintained a stable voltage profile over 2000 hours, strongly validating the feasibility of synergistic biomimetic integration for advancing flexible ZIBs under demanding operating conditions.

Building upon the previously described multi-parameter synergistic optimization of adhesion and hydrophobicity, researchers are increasingly turning to biological templates with greater structural complexity and functional integration to further advance interfacial engineering between flexible electrolytes and Zn anodes. In a representative example, Ai et al.¹⁷⁴ proposed a dual-function biomimetic design inspired by the hierarchical “brick–mortar” architecture of nacre and the ion-selective transport of cellular membranes, aiming to simultaneously enhance mechanical integrity and interfacial ion dynamics (Fig. 14d). In this strategy, two-dimensional mesoporous polydopamine (2D-mPDA) platelets were assembled into an ordered lamellar superstructure, mimicking the nacreous layering seen in mollusk shells. This ordered structure significantly enhanced the elastic modulus to 4.69 GPa, over fivefold higher than that of its conventional 3D-mPDA counterpart (0.93 GPa). A dense hydrogen-bonding network formed between adjacent nanosheets, providing robust interfacial cohesion that effectively suppressed Zn dendrite propagation and resisted mechanical deformation during cycling. To complement this mechanical reinforcement, a vertically aligned ion channel membrane (∼8.6 nm pore size) was constructed to mimic biological ion-selective membranes. This design facilitated high ionic conductivity (40.6 mS cm⁻¹) while promoting strong coordination between Zn²⁺ and –OH/–NH functional groups. These interactions significantly lowered the desolvation energy of [Zn(H₂O)₆]²⁺ from 0.943 eV to 0.465 eV and reduced the overall activation energy for Zn²⁺ transport from 44.0 to 23.5 kJ mol⁻¹. As a result, the system minimized fluctuations in interfacial current density and Zn²⁺ concentration gradients, enabling more uniform ion migration and stable electrochemical reactions. This integrated biomimetic strategy achieved comprehensive performance enhancements across mechanical, ionic, and interfacial dimensions. Compared to the control, the cycling life was extended from 161 to 580 h at 20 mA cm⁻² and Zn nucleation overpotential was reduced to 35 mV, with 99.8% CE retained after 1500 cycles. These results strongly validate the engineering feasibility and practical potential of this hierarchical bioinspired approach for flexible ZIBs. More broadly, this work exemplifies how integrative biomimicry can offer a powerful design paradigm to overcome multi-parameter optimization challenges in aqueous ZES devices.

Table 1 partially illustrates the application of biomimetic designs in various components of ZIBs. The studies reviewed demonstrate that integrating natural selection-inspired mechanisms into electrode materials, separators, and electrolytes significantly enhances the electrochemical performance of ZIBs. Specifically, advances in cathode material structure and morphology, suppression of side reactions in the anode, superior ionic conductivity and selective permeability in separators, and enhanced conductivity and stability in electrolytes have all been achieved by drawing inspiration from biological systems. These innovations have led to the development of ZIBs with remarkable electrochemical performance. In conclusion, emulating advanced biological mechanisms and structural designs has markedly improved the overall performance of ZIBs. This interdisciplinary innovative approach opens new avenues for designing high-performance, cost-effective, and environmentally friendly energy storage technologies. Future research involves the development of cost-effective biological mechanisms and materials to achieve even more efficient and stable ZIBs, capable of meeting the increasing global energy demands.

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3. Zinc–air batteries

The concept of ZABs was first proposed by L. Maiché in 1878.¹⁷⁷ However, early designs employing acidic electrolytes suffered from severe instability, limiting their initial adoption. A major breakthrough occurred in 1932 when George W. Heise and Erwin A. Schumacher replaced the acidic electrolyte with an alkaline one, making a turning point in the development of ZABs (Fig. 15a).²¹ Nevertheless, the sluggish kinetics of the ORR/OER at the cathode during charge/discharge cycles significantly reduces their practical energy density. Additionally, the considerable mass of conventional electrodes further constrains their application in portable or lightweight devices.^30,178 Although platinum-based ORR catalysts and iridium (Ir)/ruthenium (Ru)-based OER catalysts have achieved commercialization, their high preparation cost and relatively poor stability in practical applications have hindered widespread adoption.^179,180 In response to these issues, research has intensified on the development of low-cost, bifunctional ORR/OER catalysts with high activity and durability, which are essential for advancing next-generation ZAB technologies.¹⁸¹ Unfortunately, the development of ZABs stagnated as LIBs emerged with superior performance and advanced research focus, overshadowing ZAB advancements.¹⁸² Over time, the rapid development of LIBs revealed critical limitations, including uneven distribution of Li resources, safety concerns, and high costs.¹⁸³ With advancements in research technologies and the growing demand for safer, high-energy-density electronic devices, ZABs have re-emerged as a promising technology. Their high theoretical density, intrinsic safety, and resource abundance have reignited interest, driving rapid developments in ZAB research and applications (Fig. 15b).

The ZABs are a class of metal–air batteries that utilize O₂ from the air as the active cathode material. Electricity is generated through a redox reaction between Zn at the anode and O₂ at the cathode. Owing to their high theoretical energy density, low cost, and environmental compatibility, ZABs are considered strong contenders for next-generation energy storage systems. A typical ZAB comprises an air cathode, a Zn anode, a separator, and an electrolyte.¹⁸⁵ The anode and separator are similar to those used in ZIBs, with the anode commonly fabricated from Zn foil or sheet and the ion-exchange membrane (IEM) functioning to prevent direct contact between the electrodes while allowing ionic transport. Furthermore, ZABs generally operate in concentrated alkaline electrolytes, such as KOH or NaOH solutions. Comparative studies show that KOH is preferred due to its lower viscosity, higher O₂ diffusivity and solubility, and superior ionic conductivity compared to NaOH. The ionic conductivity of K⁺ (73.50 Ω⁻¹ cm⁻² equiv.⁻¹) significantly exceeds that of Na⁺ (50.11 Ω⁻¹ cm⁻² equiv.⁻¹).^185,186 In addition to the primary alkaline electrolyte, small amounts of Zn salts, such as zinc chloride (ZnCl₂) or zinc acetate (Zn(CH₃COO)₂), are often introduced to improve the reversibility of Zn redox reactions and enhance overall battery performance.¹⁸⁷ Among the various components of ZABs, the air electrode plays the most critical role in determining the electrochemical performance. Typically, the air cathode comprises three layers: a catalytic layer, a current collector, and a gas diffusion layer.¹⁸⁸ The catalytic layer, which governs the ORR and OER processes, is generally composed of catalytic materials, including noble metals such as platinum (Pt) and silver (Ag), non-noble metals such as Mn, iron (Fe), and Co, or their metal compounds.¹⁸⁹

As demonstrated in Fig. 15c, during battery operation in an alkaline electrolyte, redox reactions occur at the anode, while the ORR and the OER proceed at the air cathode. The electrochemical reactions are summarized as follows:¹⁸⁴

Anode: Zn + 4OH−(aq) – 2e− ↔ Zn(OH)42−(aq) (Eθ = −1.25 V vs. SHE)	(R8)

Cathode: O2(g) + 2H2O(l) + 2e− ↔ 4OH−(aq) (Eθ = 0.40 V vs. SHE)	(R9)

Overall: 2ZnO ↔ O2(g) + 2Zn	(R10)

As demonstrated by the reaction formula above, ZABs possess a theoretical open-circuit voltage of 1.65 V. Nevertheless, the multistep ORR introduces substantial overpotentials, resulting in a practical operating voltage significantly higher than the theoretical value. This energy dissipation underscores the critical need for the development of efficient air cathode materials to minimize polarization and enable widespread adoption of ZABs. As research progresses, the working mechanism of ZABs has been gradually clarified, with the interplay of the ORR and the OER at the electrodes being the primary factor. Among them, the ORR is more prone to occur under neutral and alkaline conditions (Fig. 16a).¹⁹⁰ The ORR reaction is comprised of several steps, including substance adsorption, electron transfer, ion transfer, bond breaking and bond generation, and substance resolution. Taking the most common alkaline electrolyte as an example, its ORR reactions follow either a four-electron pathway (4e⁻ pathway, Griffith mode) or a two-electron pathway (2e⁻ pathway, Pauling mode). The 4e⁻ pathway, which achieves a higher O₂ utilization efficiency, involves a multi-step proton-coupled electron transfer process with the formation of various intermediate species (Fig. 16b).

The reaction equations for the 4e⁻ pathway are provided below (* represents the catalytic active site):¹⁹¹

* + O2(g) + H2O(l) + e− → *OOH + OH−(aq)	(R11)

*OOH + e− → *O + OH−(aq)	(R12)

*O + H2O(l) + e− → *OH + OH−(aq)	(R13)

*OH + e− → * + OH−(aq)	(R14)

O₂ from the air enters the electrode and binds to the active sites on the catalyst, forming adsorbed oxygen species (O₂*). This species undergoes reduction to produce *OOH, and the O–O bond in *OOH subsequently breaks to generate O*, which combines with H₂O to form *OH. Finally, the *OH desorbs from the catalyst surface, completing the reaction process. In contrast, the 2e⁻ pathway follows these reaction equations:

O2(g) + H2O(l) + 2e− → HO2−(aq) + OH−(aq)	(R15)

HO2−(aq) + H2O(l) + 2e− → 3OH−(aq)	(R16)

The peroxide (HO₂⁻) produced via the 2e⁻ pathway can corrode the electrode, leading to rapid degradation of battery performance and posing significant safety risks. Consequently, designing cathode catalyst materials that promote the 4e⁻ pathway has become a primary focus of research to improve the performance and safety of ZABs.

During the charging process of ZABs, the OER faces severe catalytic challenges. Although noble metal oxides such as RuO₂ and IrO₂ are widely recognized as benchmark OER catalysts, their large-scale application remains constrained. The scarcity and high cost of noble metals significantly hinder economic viability. Moreover, under strongly oxidative operating conditions, these catalysts are susceptible to surface reconstruction, lattice oxygen loss, and nanoparticle agglomeration, all of which diminish the density of active sites and disrupt electron transport pathways. Consequently, the development of cost-effective synthesis methods for highly stable OER catalysts has emerged as a critical research priority. Based on the types of OER catalysts, the mechanisms can be divided into two types: the adsorbate evolution mechanism (AEM) and the lattice oxygen mediated mechanism (LOM).^192,193

(1) Adsorbate evolution mechanism (AEM)

In the AEM, the OER proceeds via a series of proton–electron transfer reactions at the metal active sites, typically involving four key steps:¹⁹⁴

* + OH−(aq) → *OH + e−	(R17)

*OH + OH−(aq) → *O + H2O(l) + e−	(R18)

*O + OH−(l) → *OOH + e−	(R19)

*OOH + OH−(aq) → * + O2(g) + H2O(l) + e−	(R20)

Initially, OH⁻ is adsorbed at the active site to form *OH. Subsequent deprotonation yields *O, followed by the formation of *OOH through O–O bond coupling and finally the release of O₂ with the regeneration of the active site (Fig. 17a). To assess the energetics of each reaction step under an applied external voltage (U), the corresponding free energy changes (ΔG) are calculated by including the term −eU.¹⁹⁵ The free energy calculation steps for the four reactions are as follows:

ΔG1 = ΔGHO* − ΔG* + 1/2GH2(g) − eU	(R21)

ΔG2 = ΔGO* − ΔGHO* + 1/2GH2(g) − eU	(R22)

ΔG3 = ΔGHOO* − ΔGO* + 1/2GH2(g) − eU	(R23)

ΔG4 = ΔGO2(g) + ΔG* − ΔGHOO* + 1/2GH2(g) − eU	(R24)

Theoretically, the step requiring the highest free energy is pivotal in determining the minimum activation energy barrier for the OER. In an ideal scenario, all steps would require equal free energy (1.23 eV) under standard conditions (U = 0), leading to a theoretical zero overpotential.^196,197 However, this is unachievable in practice due to disparities in intermediate adsorption strengths, anisotropic surface activity, and solvation effects. Empirically, the first and fourth steps show a linear scaling relationship, with a nearly constant energy difference (ΔG_HOO* − ΔG_HO*) of 3.2 ± 0.2 eV, limiting the extent of independent optimization for each step. From this, the theoretical minimum overpotential can be derived as 0.37 eV, corresponding to a total Gibbs energy requirement of 2.46 eV for the full OER process (Fig. 17b).¹⁹⁸ Hence, the catalytic performance of OER materials can be evaluated based on the descriptor of (ΔG_O* − ΔG_HO*), and the corresponding overpotential is defined as [η^OER = {max[(ΔG_O* − ΔG_HO*), 3.2 eV − (ΔG_O* − ΔG_HO*)]/e} − 1.23 V].¹⁹⁹ According to the Sabatier principle,²⁰⁰ optimal catalytic activity arises when the adsorption strength of intermediates is neither too strong nor too weak. This forms the basis for volcano-type plots that relate η^OER and (ΔG_O* − ΔG_HO*) (Fig. 17c), guiding the design of high-performance catalysts through active site engineering and surface modification to tune this critical descriptor toward the ideal 1.6 eV.²⁰¹

(2) Lattice oxygen mediated mechanism (LOM)

To account for phenomena that cannot be fully explained by the conventional AEM, the lattice oxygen-mediated mechanism (LOM) has been proposed. This mechanism involves the direct participation of lattice oxygen, accompanied by reversible formation of surface oxygen vacancies (V_O) in transition metal oxides. DFT calculations have clarified the LOM catalytic pathway (Fig. 17d), which, like the AEM, consists of four steps. The proposed reaction steps are as follows:^184,202,203

*OH + OH−(aq) → (VO + *OO)† + H2O(l) + e−	(R25)

(VO + *OO)† + OH−(aq) → O2(g) + (VO + *OH)† + e−	(R26)

(VO + *OH)† + OH−(aq) → (OH− + *OH)† + e−	(27)

(OH− + *OH)† + OH−(aq) → *OH + H2O(l) + e−	(28)

The reaction initiates with the coupling of *OH and OH⁻, undergoing dehydrogenation to form a superoxo-like *OO species and a surface V_O. The *OO species subsequently releases O₂ while regenerating *OH. This is followed by the reoccupation of the V_O site by a new *OH species, which induces protonation of an adjacent lattice oxygen atom. Upon deprotonation, the *OH intermediate is restored, thus completing the catalytic cycle. Unlike the AEM pathway, the LOM bypasses the *OOH step entirely and enables direct coupling between (VO + *OO)^† and OH⁻ to generate O₂. Moreover, while the AEM is predominantly driven by cation-centered redox processes, the LOM involves the redox activity of lattice oxygen itself. Effective implementation of the LOM pathway requires sufficient lattice oxygen mobility and reactivity, which can be promoted by enhancing metal–oxygen covalency or introducing oxygen-deficient active sites. These strategies facilitate the formation and stabilization of reactive oxygen species and accelerate OER kinetics in transition metal-based electrocatalysts.

3.1 Cathodes

The air electrode, as a key determinant of the electrochemical performance of ZABs, requires careful design to optimize its structure, morphology, and functionality. Enhancing the bifunctional catalytic activity of the air electrode is essential to ensure excellent conductivity, efficient gas diffusion, structural stability, and long-term durability.²⁰⁴ Additionally, the growing emphasis on lightweight and portable energy storage systems has driven advancements in material design to minimize the weight of electrode materials. In ZABs, the weight of the electrode materials directly affects overall performance, with lightweight designs contributing to reduced device weight, improved energy efficiency, and extended runtime. To achieve these goals, it is crucial to optimize the composition and structure of electrode materials, balancing lightweight design with the necessary mechanical strength and conductivity.²⁰⁵ This requires a comprehensive approach to material design, considering multiple factors to achieve an optimal balance between performance, stability, and portability.

In the development of lightweight electrode designs, the performance of the catalyst remains a critical evaluation criterion. Bifunctional oxygen catalysts need to exhibit excellent performance across several parameters, including overpotential, Tafel slope, exchange current density (j₀), turnover frequency, and stability. These metrics not only assess the catalytic activity but also determine the practicality and efficiency of the catalyst in real-world applications. Among these, overpotential serves as a key indicator of catalytic activity, representing the deviation between the operating potential and the thermodynamic equilibrium potential. The overall catalytic activity of the catalyst is commonly evaluated using the formula ΔE = E_j10 −E_1/2, where E_j10 is the potential at a current density of 10 mA cm⁻² and E_1/2 is the half-wave potential. The Tafel slope, another critical parameter, provides an intuitive measure of the catalyst kinetic performance; a lower Tafel slope indicates faster reaction kinetics and better catalytic activity. The Tafel slope is determined using formula (3):

	(3)

where η represents the overpotential, j₀ denotes the exchange current density, j refers to the current density, and b is the Tafel slope. The exchange current density (j₀) is a critical parameter influenced by factors such as electrode material, temperature, and electrolyte concentration, and it serves as an indicator of the electrode catalytic activity. Turnover frequency (TOF) is another essential metric, reflecting the intrinsic activity of the material by measuring the rate of product formation per active site. Stability, on the other hand, is a crucial determinant of the lifespan of electrode material; catalysts with better stability are associated with longer operational lifetimes, ensuring sustained performance under practical conditions.

With advancements in technology, nature continues to provide profound inspiration for addressing complex challenges in engineering and materials science, driving the development of innovative technologies. By integrating biomimetic principles with the aforementioned performance indicators, bifunctional oxygen catalysts can be comprehensively optimized in terms of structure, composition, functionality, and fabrication processes. This approach enables the design of efficient, stable, lightweight, and cost-effective catalysts, significantly enhancing the performance of ZABs while also offering innovative solutions for other electrochemical energy storage systems. Future research can focus on exploring novel bionic structures and mechanisms to further improve the comprehensive performance of catalysts. To elucidate the role of biomimetics in ZAB electrode materials, this section classifies the electrode materials into four categories: metal-free carbon-based materials, carbon-free metal-based materials, carbon-supported nanoscale materials and carbon-supported atomic materials. A detailed overview of the current research progress and future development trends in each category is provided, highlighting the potential for further innovation in this field.

3.2 Anodes

In ZABs, when the catalytic activity of the air cathode and the O₂ diffusion rate meet performance requirements, the battery capacity limit is primarily determined by the anode material. Similar to ZIBs, challenges such as electrode corrosion, HER, Zn dendrite growth, and passivation remain significant concerns for the anode in ZABs.²³⁵ As the potential applications of ZABs continue to be expand, the performance requirements for these batteries have also increased. However, the performance of the Zn anode in most electrolytes has yet to meet these expectations, underscoring the practical importance of developing a stable Zn anode for ZABs. Biomimetics, an innovative approach inspired by the structures and functions of natural species, offers a promising pathway for achieving long-term stability and enhanced performance in Zn anodes. Despite its potential, biomimetic research on Zn anodes for ZABs remains relatively limited. The following examples illustrate the significant practical value of employing biomimetic design to optimize Zn anode stability and improve overall battery performance.

Rechargeable ZABs, often referred to as “breathable” batteries,²³⁶ have inspired innovative strategies for improving electrochemical performance by mimicking the respiratory mechanisms of terrestrial animals. In animals, breathing primarily relies on the lungs creating a pressure differential to facilitate gas exchange. O₂ exchange occurs on the surface of alveoli, where the large specific surface area provided by billions of alveoli enable efficient, rapid, and stable O₂ transfer. Moreover, the alveoli are protected from external damage by their internal location, isolated from the external environment.²³⁷ Drawing inspiration from the working mechanism of alveoli, Li et al.²³⁸ developed a solid-state electrolyte (PVA-lecithin) by modifying the polyvinyl alcohol (PVA) gel with lecithin (Fig. 22a). This design achieved high water retention, enhanced stability, and improved electron transfer rates. The construction of a stable interface significantly inhibited the formation of reactive oxygen species (ROS), effectively suppressing side reactions on the Zn anode surface. When incorporated into a ZAB, the solid-state electrolyte doubled battery lifespan, providing a promising new approach for developing long-cycle ZABs. In recent years, the rapid growth of wearable ZABs has heightened the demand for stable, high water-retention materials. Inspired by the water retention properties of soil, Fan et al.²³⁹ designed a carboxyl-rich superabsorbent hydrogel polymer electrolyte (SSHPE) (Fig. 22b). The synergistic interaction between hydrogen bonds formed by water molecules and carboxyl groups, along with the carefully engineered porous structure, significantly enhanced the absorption and water retention capabilities of the SSHPE. Additionally, the electrostatic interactions between the carboxyl groups and the Zn anode promoted the formation of a dendrite-free interface, significantly extending the cycle life.

The development of ZABs with high safety, energy density, and environmental adaptability is a critical direction for future research. However, harsh environmental conditions, particularly low temperatures, can cause a rapid decline in the lifespan of ZABs, ultimately leading to failure. Low temperatures, a common challenge for aqueous batteries, induce issues such as electrolyte freezing, sluggish reaction kinetics, and increased interfacial resistance, which severely limit the performance and durability of ZABs in cold environments. As a result, advancing ZAB technology suitable for low-temperature environments has emerged as a significant research focus. To overcome these challenges, researchers have drawn inspiration from nature. For instance, animals like penguins thrive in Antarctica, where temperatures can drop below −40 °C, thanks to a thick layer of insulating fat that enables their survival in extreme cold.²⁴¹ Inspired by this antifreeze mechanism, Deng et al.²⁴⁰ developed a gel polymer electrolyte (AGC-T) that mimics the protective function of fat (Fig. 22c). By tailoring the interaction between anions and H₂O, this electrolyte enabled uniform Zn deposition and rapid ion transport even at low temperatures. The AGC-T electrolyte supported long-term cycling under high current densities, demonstrating 120 hours at 50 mA cm⁻² at 25 °C and 205 hours at 10 mA cm⁻² at −40 °C. 3D laser confocal scanning microscopy (3D CLSM) tests revealed that the Zn anode surface roughness using AGC-T (14.437 μm) was significantly lower than that with AGC (35.9 μm) under identical conditions, further validating the relationship between uniform Zn deposition and superior battery performance. Moreover, DFT calculations further supported the improved performance by showing a stronger interaction energy between [CF₃SO₃]⁻ and H₂O (−0.205 eV) relative to [ClO₄]⁻ and H₂O (−0.171 eV). This enhanced anion-solvent binding suggests tighter coordination of Zn(CF₃SO₃)₂ with water molecules, stabilizes the solvation environment and suppresses parasitic side reactions. By learning from nature, the occurrence of side reactions on the Zn anode surface in ZABs, such as Zn dendrite growth, hydrogen evolution, and Zn dissolution, was effectively mitigated. These biomimetic design strategies have facilitated the development of innovative materials that enhance performance and stability, even under extreme conditions.

By emulating these natural mechanisms, significant progress has been made in mitigating side reactions on the Zn anode surface in ZABs. These advancements enhance cycling stability and energy density while extending the operational lifespan of the batteries. This biomimetic approach offers innovative ideas and technical pathways for the development of efficient and safe ZABs. By leveraging the principles of nature, this strategy highlights the potential of applying biological inspiration to modern battery technology, contributing to the advancement of sustainable energy solutions.

3.3 Separators

The separator is a critical component of ZABs, serving a function similar to that in ZIBs by separating the cathode and anode, preventing short circuits and facilitating the passage of specific ions. However, the separator in ZABs must address unique challenges, making their design and material selection distinct from those used in ZIBs.¹⁶⁸ These challenges include the need to control O₂ diffusion, retain water, resist dendrite penetration, withstand chemical corrosion, and maintain long-term stability.²⁴² Overcoming these challenges is essential for promoting the widespread adoption of ZABs in energy storage applications. Given these requirements, bioinspired design offers a promising strategy to enhance the performance of ZAB separators. By mimicking natural structures and mechanisms, bioinspired designs can significantly enhance the multifunctionality of separators to meet the specific demands of ZABs. For instance, Xu et al.²⁴³ successfully prepared an anion exchange membrane (AEM) using a hydrothermal process to interweave Co₃O₄/MnO₂ onto CNTs (Fig. 23a). The chrysalis-like morphology and coupling effects synergistically enhanced the bifunctional oxygen catalytic activity and facilitated electron transfer. Additionally, the structural design imparted excellent flexibility to the electrode material, allowing it to maintain functionality even after multiple bends. O₂-selective membranes with high O₂ permeability also serve as primary bioinspired models for ZAB separators. These membranes align with the working mechanism of ZABs, which require efficient O₂ transport for energy generation. Olga et al.²⁴⁴ mimicked the O₂-selective membranes found in alveoli by incorporating iron phthalocyanine (FePc) onto a polypropylene (PP) and stainless substrate to control pore structure and morphology (Fig. 23b). Adjusting the FePc content not only optimized O₂ permeability but also enhanced liquid retention capabilities. These examples highlight how learning from nature can effectively enable the design and fabrication of functional separators tailored to meet the specific requirements of ZABs, advancing their performance and reliability for energy storage applications.

3.4 Electrolytes

The electrolyte, often referred to as the “blood” of batteries, has always been a focal point of research. In ZABs, alkaline aqueous solutions such as potassium hydroxide (KOH) are commonly used as electrolytes. However, as ZABs evolve to meet the increasing demands of practical applications, the need for innovative electrolyte solutions becomes more critical. Drawing inspiration from nature has emerged as a promising approach for advancing ZAB electrolytes. In the design of solid-state electrolytes for flexible ZABs, it is often difficult for a single biomimetic parameter to simultaneously meet the multiple performance requirements of mechanical strength, water retention, and ionic conductivity. Therefore, the synergistic optimization of multiple biomimetic parameters has become a key strategy. In a representative study, Dou et al.²⁴⁵ developed a dual-penetrating network solid-state electrolyte (MC/PAM–PDMC) by drawing inspiration from two distinct biological systems: the “rigid-flexible” architecture of collagen and elastin in animal dermis, and the water-retention mechanism of plant cell vesicles (Fig. 23c). The system integrates a dynamic double-network composed of a rigid ionic polymer PDMC and flexible PAM hydrogel, mimicking the supramolecular interplay between collagen fibers and elastin strands. This hybrid design achieved impressive mechanical properties, with a tensile strength of 230 kPa and an elongation at break of 1800%, both substantially higher than those of the PDMC single-network control (23.7 kPa, 140%). Functionally, PDMC provided mechanical reinforcement and formed continuous OH⁻ conduction pathways, while PAM contributed flexibility via hydrogen bonding interactions. To further mimic natural water management systems, hollow polymer microcapsules (MCs) were incorporated as artificial “water reservoirs,” emulating the vesicle-based water storage of plant cells. These MCs enhanced water uptake and retention through capillary forces and molecular interactions, achieving a remarkable water absorption capacity of 107.5 g g⁻¹. In addition, the high-density surface hydroxyl groups on the MCs effectively shortened OH⁻ diffusion paths, contributing to an ultrahigh ionic conductivity of 215 mS cm⁻¹. The synergistic coupling of the dual-network matrix and MC inclusions resulted in refined pore architecture, enhanced structural stability, and improved ion–water transport pathways. This also led to a high interfacial adhesion strength with the Zn anode (>200 kPa), which effectively suppressed interfacial delamination and electrochemical degradation during long-term operation. As a result, the flexible ZABs assembled with this bioinspired electrolyte exhibited an open-circuit voltage of 1.47 V, a high specific capacity of 758 mAh g⁻¹, and retained over 90% of capacity after 300 cycles under a tight bending radius of 2 mm. This study exemplifies how multi-parameter biomimetic integration can deliver simultaneous improvements in mechanical, ionic, and interfacial performance, providing a compelling paradigm for next-generation flexible ZAB design.

Nature, as an integrated system, continues to provide effective solutions to the practical challenges faced in ZAB applications, leading to significant overall performance improvements. This is particularly evident in the field of robotics, a rapidly advancing area in today society. Robots require energy supply systems with reduced weight and volume to enhance efficiency, safety, and cost-effectiveness. Inspired by the human body's fat storage mechanism, which cushions external impacts and provides energy reserves, Wang et al.²⁴⁶ developed a groundbreaking concept (Fig. 23d). By using high-safety, high-energy-density ZABs as the “skin” of the robots, they reduced the need for separate batteries while simultaneously providing protection and energy supply. The implementation of this concept, using Kevlar 69 microfibers composite materials, effectively mitigated side reactions and achieved a stable energy supply for over 100 hours. The assembled ZABs demonstrated excellent flexibility and mechanical stability, powering worm-like and scorpion-like robots, thus demonstrating the potential for integrating ZABs into robotics to address weight and volume challenges.

Biomimetics, as an innovative efficient learning method approach, effectively enhances performance by emulating the structures and functions of natural organisms in nature. Table 2 partially lists the applications of biomimetic design in various components of ZABs. The aforementioned findings highlight the significant impact of biomimetic design on improving the application of biomimicry in various components of ZABs, revealing that biomimetic design can significantly improve the performance of ZABs. By addressing existing technological challenges, biomimetic strategies open new avenues for advancing efficient and sustainable energy storage technologies; they help to overcome existing technological bottlenecks and offer new directions for future research on efficient and environmentally friendly energy storage technologies. Continued exploration of biomimetics in this field of research is expected to overcome key bottlenecks of ZABs, bringing these batteries closer to commercial applications. This progress is anticipated to make a substantial contribution to the development of clean energy solutions, fostering the transition to sustainable energy systems.

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4. Other zinc-based batteries

4.1 Cathodes

With the continued development of ZIBs and ZABs, Zn metal-based battery systems have carved out a distinct niche in the energy storage landscape. ZIBs are particularly well-suited for grid-scale energy storage and portable electronics due to their use of aqueous electrolytes, which offer intrinsic safety, high theoretical capacity and cost-effectiveness. Energy storage in ZIBs is achieved via the reversible intercalation/deintercalation of Zn²⁺ into Mn- or V-based cathodes, enabling excellent cycling stability without the need for complex sealing protocols. However, critical challenges, such as Zn dendrite formation at the anode and cathode dissolution or structural degradation, continue to hinder their applications in high-energy-demand scenarios. Complementing ZIBs, ZABs present transformative potential owing to their open-air cathode architecture, which utilizes atmospheric O₂ as the active material. This configuration provides a theoretical energy density approximately five times greater than that of LIBs. The incorporation of a gas diffusion electrode facilitates efficient three-phase (gas/liquid/solid) interfacial reactions, demonstrating promising applicability in unmanned aerial vehicles and electric mobility. Despite these advantages, several technical obstacles remain, particularly the sluggish kinetics of ORR/OER reactions, electrode passivation due to electrolyte salt crystallization, and humidity sensitivity of air cathodes, which must be addressed to fully realize the potential of ZABs in practical applications. To overcome these limitations and broaden the scope of Zn-based energy storage, several emerging Zn-based battery systems have garnered increasing attention. Notable examples include ZCBs, zinc–organic batteries (ZOBs), ZBBs, and Zn–iodine batteries, each offering unique electrochemical mechanisms and application prospects (Fig. 24).

The ZCB system achieves dual environmental and energy benefits through electrocatalytic CO₂ reduction reactions (CO₂RR). During the discharge process, these systems not only generate electricity but also convert atmospheric CO₂ into value-added chemicals, such as formic acid (HCOOH) and methanol (CH₄O), thereby enabling simultaneous carbon capture, utilization, and energy delivery.²⁴⁷ As shown in Fig. 24a, a typical aqueous rechargeable ZCB consists of a Zn foil anode and a gas diffusion cathode loaded with transition metal catalysts (Fe, Co, Ni or Cu) for selective CO₂ conversion. Unlike conventional ZIB or ZAB systems, the electrolyte of the ZCBs consisting of Zn²⁺ and alkaline components (KOH/KHCO₃) simultaneously enhances CO₂ solubility and facilitates fast CO₂ transport kinetics. A unique feature of ZCBs is the use of a bipolar membrane as the separator, which enables the separation of electrolytes with different pH values on the anode and cathode sides. This configuration supports directional transport of protons (H⁺) and hydroxide ions (OH⁻) under an applied electric field, thereby optimizing the ionic environment for both Zn electrochemistry and CO₂RR.

Taking HCOOH as a representative product, the discharge process in a ZCB can be described by the following reactions:

Anode (alkaline electrolytes): Zn – 2e− → Zn2+	(R29)

Zn2+ + 4OH− → Zn(OH)42−	(R30)

Zn(OH)42− → ZnO + H2O + 2OH−	(R31)

	(R32)

	(R33)

Cathode: CO2 + 2H+ + 2e− → HCOO	(R34)

	(R35)

	(R36)

Overall: Zn + CO2 + 2H+ + 4OH− → HCOOH + Zn(OH)42−	(R37)

EDischarge = Ec − Ea = 0.95 V vs. SHE	(R38)

These electrochemical equations demonstrate that ZCBs not only enable the generation of electrical energy but also facilitate the electrochemical conversion of CO₂ into value-added products. As a result, the effective capture and utilization of CO₂ have become urgent priorities in both environmental and energy research.²⁴⁸ The primary working mechanism involves the reversible conversion between CO₂ and HCOOH during the CO₂RR process, forming the basis of the battery charge–discharge cycle. Unfortunately, the inherent stability of the CO bond and the occurrence of side reactions result in low CO₂RR efficiency,¹⁰⁸ hindering large-scale production and application. To address these challenges, Li et al.²⁴⁹ drew inspiration from the unique 3D structure of thistles and the self-protection mechanism of plant waxes. They used conductive PPy as a plant wax analogue to protect the internal sea-urchin-like bismuth sulfide (Bi₂S₃), successfully synthesizing a 3D composite material (Bi₂S₃–PPy) enriched with S vacancies (Fig. 25a). This unique structure provided the material with an extremely high specific surface area, exposing more active sites. Additionally, the introduction of S vacancies optimized the electronic structure, significantly enhancing the CO₂ capture capability and conductivity of the material. DFT calculations further revealed that the introduction of S vacancies lowered the formation energy of intermediates (*OCHO), enhancing the catalytic performance. When applied to ZCBs, the Bi₂S₃–PPy composite demonstrated remarkable long-term stability for 110 hours and achieved a maximum power density of 2.4 mW cm⁻².

Although inorganic electrode materials such as V, Mn, and Co are widely used as cathodes for Zn-based batteries due to their good electrochemical performance, they present notable drawbacks such as resource scarcity and high energy consumption required for their production. Additionally, repeated ion insertion and extraction processes in inorganic materials can lead to volume expansion, which may cause lattice fragmentation and significantly reduce the lifespan of energy storage devices. In contrast, organic materials, primarily composed of low-cost, abundant non-metallic elements such as C, N, and O, offer distinct advantages. They can effectively avoid the volume changes associated with inorganic materials through coordination reaction mechanisms. In zinc–organic batteries (ZOBs), organic electrodes can be classified into three types based on the redox characteristics of their active functional groups: n-type, p-type, and bipolar-type materials (Fig. 24b). n-type materials, such as those containing carbonyl (CO) and imine (CN) groups, store charge by coordinating cations via enolization reactions. p-type materials, including triphenylamine derivatives and organosulfur polymers, operate through the coordination of anions facilitated by electron-deficient states. Bipolar-type electrodes, typically conjugated polymers with dual redox active sites that enable both oxidation and reduction reactions, allow for ambipolar charge storage. Taking quinone-based materials as a representative example, the electrochemical reaction during charge/discharge cycling can be expressed as:

Discharge: –CO– + e− → –C–O–	(R39)

Charge: –C–O– – e− → –CO–	(R40)

During discharge, the carbonyl oxygen is reduced upon accepting an electron, followed by coordination with cations (H⁺ or Zn²⁺) from the electrolyte, resulting in energy release. In the reverse charging process, the reduced intermediates are oxidized through electron removal, accompanied by the dissociation of the cations, thereby restoring the original CO functional groups. This energy storage process relies on the reversible redox conversion of the organic cathode materials between oxidized and reduced states via electron gain and loss.²⁵⁰ However, ZOB cathode materials often face challenges such as low activity and insufficient structural stability, leading to limited energy density and short cycle life. To address these challenges and develop ZOBs with superior electrochemical performance, Song et al.²⁵¹ designed a flower-like nano-carbon substrate loaded with dinitrobenzene (p-DB) as the cathode material for ZOBs (Fig. 25b). The bionic flower-like morphology provided a high surface area and structural stability, while the incorporation of electron-withdrawing nitro groups facilitated energy level modulation, promoting efficient and reversible redox activity. This synergistic design effectively suppressed the dissolution of active materials into the electrolyte and enhanced the redox kinetics of the nitro groups. As a result, the optimized ZOB exhibited excellent long-term cycling stability over 25000 cycles and achieved a high specific capacity of 402 mAh g⁻¹.

Although ZOBs have demonstrated promising energy densities and theoretical efficiencies, several challenges, such as electrolyte instability, limited cycle life, and the need for electrode material optimization, continue to hinder their practical deployment. As an alternative, ZBBs have emerged as a compelling solution, offering higher energy density, low-cost bromine utilization, and environmentally friendly aqueous electrolytes (Fig. 24c). Typically, ZBBs operate through a redox mechanism involving reversible Zn deposition/dissolution at the anode and bromide/polybromide conversion reactions at the cathode, described by the following half-cell and overall reactions:

Anode: Zn – 2e− ↔ Zn2+ (Eθ = −0.76 V vs. SHE)	(R41)

Cathode: Br2 + 2e− ↔ Br2+ (Eθ = 1.08 V vs. SHE)	(R42)

Overall: Zn + Br2 ↔ Zn2+ + 2Br−	(R43)

Currently, ZBBs can be broadly categorized into static and flow battery configurations. However, several technical issues persist, including kinetic incompatibility between the cathode and anode reactions, as well as the high volatility of bromine, which compromises cycling stability. To suppress bromine volatilization and shuttle effects, researchers have employed porous carbon hosts to immobilize liquid bromine and introduced quaternary ammonium salts, such as N-methyl-N-ethylmorpholinium bromide, to form stable polybromide complexes (Br₃⁻), effectively enhancing bromine immobilization and storage capacity. Nevertheless, the strong corrosivity of bromine readily causes structural degradation of electrodes/separators, while insufficient dynamic stability of polybromide complexes still triggers self-discharge. Although high concentration bromine-containing electrolytes improve conductivity, they also exacerbate material corrosion and elevate system costs. In parallel, Zn dendrite formation at the anode continues to limit long-term cycling performance.

Overcoming these challenges requires systematic breakthroughs in corrosion-resistant electrode materials, selective ion-conducting membranes, and optimized electrolyte formulations to improve interfacial kinetics and ensure system durability. In this context, the design of substrates with highly catalytic interfaces is critical for ZBB performance optimization. Lai et al.²⁵² addressed the sluggish Br⁻ adsorption/desorption kinetics by employing DFT calculations and developed a 3D urchin-like mesoporous titanium nitride hollow sphere (THNS) architecture with reduced bromide binding energy (Fig. 25c). The hierarchical porous structure of THNS accelerated desorption of Br⁻ during oxidation, enabling rapid regeneration of active sites and mitigating interfacial kinetic hysteresis. This design significantly enhanced catalytic efficiency and electrochemical performance, offering a promising pathway for advancing high-performance ZBBs.

ZBBs have demonstrated considerable potential for large-scale energy storage; however, inherent challenges such as bromine evaporation and corrosivity raise critical safety concerns that hinder practical deployment. In response, the development of alternative aqueous Zn-based battery systems has gained attention. Among them, Zn–I₂ batteries have emerged as a promising candidate due to their favorable redox chemistry, high theoretical capacity, and cost-effectiveness (Fig. 24d). In this system, energy is stored through the reversible redox reactions of I₂ at the cathode and Zn deposition/dissolution at the anode. The representative half-cell and overall reactions are as follows:²⁵³

Anode: Zn2+ + 2e− ↔ Zn (Eθ = −0.763 V vs. SHE)	(R44)

Cathode: I2 + 2e− ↔ 2I− (Eθ = 0.535 V vs. SHE)	(R45)

I− + I2 ↔ I3−	(R46)

I3− + 2e− ↔ 3I− (Eθ = 0.536 V vs. SHE)	(R47)

Overall: I2 + Zn ↔ Zn2+ + 2I− (Eθ = 1.298 V)	(R48)

Zn + I3− ↔ Zn2+ + 3I− (Eθ = 1.299 V)	(R49)

Iodine exhibits multiple valence states (I¹⁻, I⁰, I¹⁺, I³⁺, I⁵⁺, and I⁷⁺) and high theoretical capacity (211 mAh g⁻¹), making it highly attractive for energy storage applications.²⁵⁴ Moreover, iodine is widely available from natural sources, including seawater and I₂-rich plants such as kelp and wakame, contributing to its stable supply and low cost. However, several challenges hinder the practical deployment of Zn–I₂ batteries. The intrinsic low electrical conductivity of iodine necessitates its incorporation into highly conductive substrates to achieve high electrochemical activity.²⁵⁵ Even when immobilized, iodine can dissolve into the electrolyte, leading to active material loss and capacity fading. Dissolved iodine species can migrate to the anode via the “polyiodide shuttle effect”,²⁵⁴ where it reacts with metallic Zn to form poorly conductive ZnI₂. This compound occupies active Zn deposition sites, promoting dendrite formation and the HER,²⁵⁶ which collectively impede the development of Zn–I₂ batteries. To address these problems, Tang et al.²⁵⁷ employed an ultra-fast Joule heating (UHT) technique to fabricate a bioinspired lotus seedpod-like carbon-based composite (Fe–Ni@ACC) (Fig. 25d). In this structure, Fe–Ni alloy nanoparticles (lotus seeds) are uniformly embedded within activated CFs, which serve as the protective shell. This hierarchical structure enhances electronic conductivity and interfacial bonding and promotes the formation of abundant nanocavities through a high-temperature self-etching process. These cavities act as efficient active sites for iodine species confinement and catalytic conversion, thereby significantly improving the electrochemical performance of Zn–I₂ batteries. Biomimetic modification led to a 12.1% increase in specific surface area (from 1077.1 to 1207 m² g⁻¹), alongside the formation of an enriched micro/mesoporous network. This porous structure facilitated ion transport and provided space for I⁻ redox conversion, contributing to a 39.3% reduction in charge-transfer resistance and a 36.3% decrease in activation energy (from 55.09 kJ mol⁻¹ to 35.08 kJ mol⁻¹). Electrochemical testing revealed a 3.36% improvement in capacity retention after 48 hours of self-discharge at 20C, highlighting the material's enhanced structural stability. Complementary DFT calculations showed a d-band center closer to the Fermi level (0.11 eV), indicating stronger electronic coupling, and a lower reaction energy barrier (0.27 eV) for the I₃⁻ → I⁻ conversion, further validating the catalyst's enhanced redox activity. As a result, the Fe–Ni@ACC electrode achieved an ultra-high areal capacity of 4.05 mAh cm⁻² at 1C, underscoring the effectiveness of this biomimetic design strategy in addressing key challenges associated with multivalent redox chemistry in ZES systems.

Beyond the four above-mentioned batteries, other Zn-based battery systems have also demonstrated remarkable performance improvements through biomimetic approaches. For example, Zeng et al.²⁵⁸ synthesized a 3D flower-like ZnO@Ag composite material through a simple hydrothermal method and applied it to Zn–nickel (Zn–Ni) batteries. Inspired by the functionality of tree roots, Kang et al.²⁵⁹ prepared Ag₂O/CFP composites, which demonstrated excellent performance in Zn–Ag₂O batteries. Additionally, Pan et al.²⁶⁰ introduced a biomimetic design inspired by hemoglobin to develop Zn–polymer batteries with integrated self-oxidation and self-charging capabilities, showcasing the versatility of nature-inspired approaches in advancing next-generation ZES technologies.

4.2 Anodes

In addition to ZIBs and ZABs, emerging aqueous ZES systems (ZCBs, ZOBs, ZBBs, and Zn–I₂ batteries) offer a broader platform for realizing multifunctional energy storage integrated with green energy conversion.^261–264 Despite their varying cathode chemistries, these systems share a common technological bottleneck: the instability of the Zn anode. During cycling, the Zn anode is subject to dendritic growth, parasitic side reactions, volumetric changes, and uneven electrolyte contact, all of which severely hinder overall device performance and limit progress toward practical deployment.²⁶⁵

In the case of ZCBs, the Zn anode must support not only reversible Zn²⁺ plating/stripping, but also maintain electrochemical coupling with CO₂ reduction reaction (CO₂RR) intermediates and products at the cathode.²⁶⁶ However, pH fluctuations and by-product accumulation during the CO₂RR frequently trigger localized dissolution and re-deposition of Zn, which intensifies interfacial inhomogeneity, promotes potential fluctuations, and accelerates dendrite formation. Furthermore, in alkaline electrolytes, the formation of soluble Zn(OH)₄²⁻ complexes can lead to ZnO precipitation during cycling, resulting in anode passivation and performance decay.²⁶⁷ To address these challenges, constructing a bioinspired interfacial layer on the Zn anode has emerged as a promising strategy to improve stability and extend battery lifespan. For instance, mimicking the structure–function relationship of plant root systems, which regulate water and ion uptake via selective transport channels, enables the design of internally and externally coupled ion pathways. These architectures can spatially redistribute Zn²⁺ flux, facilitate selective adsorption, and effectively suppress localized Zn deposition and dendrite initiation.

In ZOBs, the Zn anode faces significant interfacial instability, primarily due to the dissolution of organic cathode materials. Commonly used organic redox-active compounds (quinones, imines, and dinitrobenzene derivatives) often exhibit high solubility in aqueous electrolytes.²⁶⁸ During cycling, these soluble species can migrate to the anode surface, where they participate in parasitic redox reactions and disrupt the formation or integrity of the solid electrolyte interphase (SEI). This effect is particularly pronounced in acidic or neutral environments, where dissolved organics readily induce interfacial corrosion, localized pH fluctuations, and inhomogeneous charge distribution-conditions that collectively accelerate Zn dendrite growth and compromise cycling reversibility.²⁶⁹ To address these challenges, the construction of ion-selective interfacial barrier layers on the Zn surface has emerged as a promising strategy. Such layers can effectively block the migration of dissolved organic species while maintaining Zn²⁺ transport, thereby stabilizing the Zn interface and improving reversibility.

In ZBBs, long-term anode stability is primarily hindered by Br⁻ shuttle effects, chemical corrosion, and dendritic deposition. Due to the high oxidative potential of bromine species, even in the presence of stabilizing additives such as quaternary ammonium salts, bromine can still diffuse toward the Zn anode.²⁷⁰ Upon contact, it reacts with metallic Zn to form Zn–Br⁻ composite deposits, which accelerate electrochemical corrosion and disrupt uniform Zn plating/stripping.²⁷¹ To suppress these degradation pathways, bioinspired protective layers, designed to mimic natural separation and filtration mechanisms, can serve as physical and chemical barriers. These layers limit bromine crossover, mitigate corrosive interactions, and promote more uniform ion flux at the Zn interface, thereby enhancing anode durability and overall cell stability.

In Zn–I₂ batteries, one of the most critical challenges associated with the Zn anode is interfacial poisoning induced by the iodine shuttle effect.²⁷² Highly soluble and reactive iodine species, such as I⁻ and I₃⁻, can readily diffuse across the electrolyte separator during cycling and reach the Zn anode surface. There, they participate in undesirable side reactions that lead to the formation of a passivating ZnI₂ layer. This irreversible interfacial deposition disrupts uniform Zn²⁺ plating/stripping, exacerbates dendritic growth, and promotes parasitic hydrogen evolution, ultimately compromising cell performance and cycling stability.^273,274 To address this issue, stabilizing the Zn anode interface through bioinspired design has emerged as an effective and promising strategy. Drawing inspiration from the human body self-recognition and selective absorption mechanisms for Zn homeostasis, Su et al.²⁷⁵ developed a biomimetic self-recognition interfacial layer that mimics the precise regulation of Zn²⁺ uptake in physiological systems (Fig. 26a). The interface was constructed using chondroitin sulfate (CHS), a naturally derived polyanionic biomolecule rich in functional groups that enable preferential Zn²⁺ adsorption while simultaneously repelling unwanted impurity ions. This selectivity facilitates directional Zn²⁺ transport and suppresses side reactions at the interface. Electrochemical evaluation demonstrated the effectiveness of this approach: the Zn–I₂ full cell exhibited exceptional cycling stability, maintaining consistent performance over 16000 cycles at a high current density of 3 A g⁻¹. This work underscores the potential of biomimetic interfacial engineering to address key challenges in Zn–I₂ battery systems and offers a compelling route toward the development of durable and scalable aqueous ZES technologies.

Overall, across advanced aqueous ZES systems, including the CO₂RR, organic redox chemistries, and halogen-based batteries involving multivalent iodine or strongly oxidizing bromine species, the role of the Zn anode has evolved beyond functioning as a passive ion reservoir. It now operates as a dynamic and multifunctional component that co-evolves with the electrolyte environment, reaction intermediates, and interfacial structures. The interfacial behavior of Zn is intimately coupled with redox product accumulation, pH fluctuations, and ion transport processes, making it a critical regulatory node in overall cell performance. In this context, biomimetic design strategies offer transformative opportunities. By emulating nature's mechanisms for ion recognition, selective transport, interfacial regulation, and adaptive responsiveness, bioinspired interfacial architectures can simultaneously address dendrite suppression, side reaction mitigation, and interfacial degradation. These functional interfaces not only protect the Zn anode but also enhance reaction kinetics and structural stability under harsh or fluctuating operating conditions.

4.3 Separators

In various ZES devices, the separator plays a pivotal role in dictating device performance by simultaneously ensuring physical isolation between the electrodes and facilitating selective ion transport. It not only provides mechanical support to prevent internal short circuits but also maintains ionic conductivity and interfacial stability during operation.¹⁶⁸ However, the diverse electrochemical environments and reaction mechanisms across various ZES devices impose stringent, system-specific demands on separator functionality.

In ZCBs, separators must remain chemically stable within alkaline media while managing large, multi-valent ions and gas evolution. The discharge process generates bulky Zn(OH)₄²⁻ complexes at the anode, while the cathodic CO₂RR produces a spectrum of intermediates and gaseous byproducts. Widely used commercial separators, such as polypropylene (PP) and polyethylene (PE) polyolefin membranes, offer decent mechanical integrity and chemical resistance, yet their intrinsic hydrophobicity leads to poor wettability in alkaline electrolytes and elevated interfacial resistance. Moreover, their heterogeneous pore distribution hampers the selective rejection of Zn(OH)₄²⁻ ions, permitting unwanted crossover that results in catalyst contamination and reduced cycling stability.²⁷⁶ The accumulation of CO₂RR byproduct gases (e.g., trace H₂) within separator pores can further obstruct ion transport and disrupt interfacial kinetics. To overcome these limitations, bioinspired design principles offer promising pathways. Drawing from the selective nutrient uptake mechanisms of plant root hairs, surface-functionalized separators with ion-specific affinity can be engineered to modulate species migration while maintaining ionic conductivity. Similarly, mimicking the hierarchical and gas-permeable architecture of alveolar membranes can guide the development of ordered, porous channel networks that facilitate CO₂ diffusion and modulate local concentration gradients, thereby enhancing reaction kinetics and energy conversion efficiency. These biomimetic strategies hold significant potential to address the multifaceted challenges of separator design across next-generation ZES platforms.

For ZOBs, several critical compatibility issues posed by organic electrolytes must be addressed. Unlike aqueous systems, organic solvents typically exhibit larger molecular sizes and lower dielectric constants, which hinder ion mobility and impose additional design constraints.²⁷⁷ Conventional separators such as ceramic membranes and cellulose-derived films often suffer from swelling, dissolution, or chemical degradation when exposed to organic electrolytes, compromising structural integrity and leading to eventual loss of electrode isolation. Furthermore, many organic cathode materials (e.g., quinones, imines, and aromatic compounds) undergo considerable volumetric expansion and molecular reconfiguration during redox cycling. These dynamic changes necessitate separators with exceptional flexibility and mechanical resilience to accommodate interfacial deformation while maintaining continuous ion conduction.²⁷⁸ However, most existing separators fail to simultaneously achieve chemical stability, mechanical compliance, and high ionic conductivity in organic media, thereby constraining the advancement of high-performance ZOBs. Bioinspired strategies may offer viable solutions, especially mimicking the hierarchical toughening mechanisms of collagen-elastin networks in animal tendons; flexible multilayered separators can be engineered to integrate tensile strength with solvent resistance, enhancing both mechanical adaptability and electrolyte compatibility.

In Zn–I₂ batteries, separator design is further complicated by the highly soluble and mobile nature of polyiodide species (e.g., I₃⁻ and I₅⁻), which readily shuttle through conventional membranes and undergo parasitic reactions with the Zn anode to form resistive ZnI₂ deposits.²⁷⁹ This shuttle effect not only accelerates polarization and capacity decay but also undermines CE and cycle life. Moreover, as Zn–I₂ systems typically employ aqueous electrolytes, the separator must exhibit robust hydrophilicity and high-water retention to preserve ionic conductivity. Unfortunately, commonly used polyolefin membranes are inherently hydrophobic and poorly wetted by aqueous media, resulting in suboptimal ion transport and eventual electrolyte evaporation.²⁸⁰ Compounding these issues, inhomogeneous Zn plating/stripping can generate dendritic structures that may pierce the separator and trigger internal short circuits. To mitigate these risks, biomimetic diaphragms inspired by the lamellar architecture of deep-sea mollusk shells may be engineered. Such structures exhibit intrinsic resistance to ion permeation (e.g., Cl⁻ and Br₃⁻) and can be adapted to produce dense, thermally stable layers capable of blocking polyiodide migration while simultaneously reinforcing mechanical strength and interfacial uniformity.

In ZBBs, separator design must contend with the dual challenges of bromine-induced corrosion and the bromine shuttle effect. The strong oxidative nature of bromine and its species (e.g., Br₂ and Br₃⁻) not only aggressively attacks conventional separator materials, but also facilitates active species crossover during cycling.²⁸³ The uncontrolled migration of bromine species to the Zn anode initiates parasitic redox reactions, leading to material loss, reduced CE, accelerated Zn corrosion, and dendritic growth, ultimately undermining long-term cycling stability and operational safety.²⁸⁴ To address these issues, Zhang et al.²⁸¹ developed a biomimetic separator inspired by the robust adhesive properties of mussel foot proteins. By coating a polyethylene (PE) separator with a conformal polydopamine (PDA) layer, they established a highly adherent and hydrophilic interface that mimics the catechol-based adhesion mechanism observed in marine mussels (Fig. 26b). Contact angle measurements revealed a significant decrease from 110° (bare PE) to 81.2° after PDA modification, accompanied by a 25% improvement in water uptake. These enhancements translated into superior electrolyte wettability and lower interfacial resistance. When applied in ZBBs, the biomimetic separator delivered impressive electrochemical performance, maintaining over 75% capacity retention after 2000 hours at 20 mA cm⁻². In contrast, the unmodified separator exhibited a sharp decline, with capacity dropping to 60% within 500 hours under identical conditions. The simplicity of the surface functionalization process, combined with the substantial gains in chemical durability and electrochemical longevity, underscores the potential of mussel-inspired strategies for separator engineering in halogen-rich battery systems.

4.4 Electrolytes

In various ZES systems, the electrolyte serves not only as the ion-conducting medium that governs charge–discharge behavior, but also as a key participant in interfacial reactions that dictate cycling stability, safety, and energy density.²⁸⁵ While ZIBs and ZABs have received extensive attention, emerging systems such as ZCBs, ZOBs, ZBBs, Zn–I₂ batteries, and Zn–polymer batteries (ZPBs) pose distinct and increasingly complex challenges for electrolyte design.

ZCBs typically employ alkaline electrolytes, most commonly potassium hydroxide (KOH), which provide dual transport channels for Zn²⁺ and OH⁻ to support the fundamental redox processes. However, such alkaline environments introduce multiple performance-limiting issues. The Zn anode suffers from severe corrosion and parasitic hydrogen evolution due to the high activity of solvated water molecules in the Zn²⁺ hydration shell, leading to diminished CE and shortened cycle life.²⁸⁶ Simultaneously, the CO₂RR at the cathode proceeds through a cascade of intermediates whose formation and conversion are highly sensitive to local pH, electrolyte composition, and ionic strength. Poorly optimized electrolytes can hinder CO₂RR kinetics and reduce Faradaic efficiency, while dynamic shifts in electrolyte pH during cycling can further destabilize reaction equilibria.²⁸⁷ To overcome these bottlenecks, researchers are turning to bioinspired approaches. For instance, chloroplast-like regulatory mechanisms, capable of enriching CO₂ locally and stabilizing photosynthetic intermediates, offer a compelling blueprint for improving CO₂ capture and utilization at the electrode–electrolyte interface. Similarly, mimicking the selective permeability of cell membranes through the incorporation of polar functional groups (e.g., amines and carboxylates) into electrolyte networks may enable molecular sieving and directional transport of CO₂ and reaction intermediates. These strategies hold potential to enhance reaction specificity, accelerate charge transfer, and suppress side reactions. However, the rational modulation of biomimetic parameters and the realization of synergistic multi-functional designs remain significant challenges. Future efforts must focus on the integrated tuning of structural motifs, solvation dynamics, and interfacial chemistry to unlock the full potential of biomimetic electrolytes in next-generation ZCB systems.

In ZOBs, electrolyte design must reconcile the inherent incompatibilities between organic electrode materials and the Zn anode. Organic electrolytes, typically comprising low-dielectric, large-molecule solvents such as carbonates, often exhibit sluggish ion transport and elevated internal resistance. Moreover, these solvents are prone to reductive decomposition at the Zn interface, forming unstable passivation layers that hinder Zn²⁺ mobility and compromise charge–discharge kinetics.²⁸⁸ Concurrently, organic cathodes undergo pronounced volume changes and molecular rearrangements during cycling, imposing additional demands on the electrolyte to ensure mechanical accommodation and interfacial integrity. However, most conventional organic electrolytes lack the adaptive structural features and ion-coordination capacity necessary to meet these multifaceted requirements.^289,290 To address these limitations, bioinspired strategies have been proposed, drawing on nature's sophisticated regulatory mechanisms. For example, mimicking the confined microenvironments of enzymatic active sites offers a route to designing electrolyte networks with localized structural order and specific coordination interactions. Similarly, imitating the protective roles of defense enzymes can mitigate direct contact between reactive components, thereby suppressing side reactions and enhancing long-term stability.

In ZBBs, the electrolyte must contend with the high oxidative activity and corrosiveness of bromine species. Despite the widespread use of porous glass fiber separators, their inability to withstand bromine-induced degradation remains a critical bottleneck.²⁹¹ Bromine and Br₃⁻ ions readily diffuse through separators and react with the Zn anode, leading to irreversible consumption of active materials, reduced CE, and accelerated dendrite formation.²⁹² These processes collectively impair the electrochemical reversibility and safety of the device. To mitigate the bromine shuttle effect and its associated degradation pathways, inspiration can be drawn from metalloenzymes with high substrate specificity.²⁹³ By mimicking the selective coordination capabilities of these biological systems, it is possible to develop electrolyte additives or network components that bind bromine species selectively, effectively lowering their reactivity and mobility. Such biomimetic electrolyte strategies offer a promising avenue for stabilizing the Zn interface and prolonging battery lifespan under corrosive conditions.

In Zn–I₂ batteries, engineering must address two interrelated challenges: the polyiodide shuttle effect and long-term system stability. Multivalent nature of iodine facilitates the formation of highly soluble polyiodide species (e.g., I₃⁻ and I₅⁻) in aqueous media. Driven by concentration gradients, these species readily migrate across the separator to the anode, where they undergo parasitic reactions with Zn to form electrically insulating ZnI₂.²⁹⁴ This side reaction contributes to increasing cell polarization and capacity degradation. Compounding this issue, the high-water activity in aqueous electrolytes, while beneficial for ionic conductivity, promotes Zn corrosion and hydrogen evolution, further undermining anode stability.²⁹⁵ To address these limitations, bioinspired design has offered promising solutions. Drawing inspiration from the layered and multifunctional architecture of human skin, a biological barrier capable of selective transport and environmental isolation, Zhang et al.²⁸² developed a “skin-inspired” asymmetric quasi-solid-state electrolyte (skin-QSSE) based on aramid nanofibers (PPTA) (Fig. 26c). Mimicking the epidermal function, the outer PPTA layer serves as a robust physical shield, while the internal amide-rich (–CO–NH–) gel matrix facilitates ion regulation and water retention. This bioinspired configuration achieved a substantial reduction in the Zn²⁺ desolvation energy barrier (−0.66 eV vs. 7.09 eV for liquid electrolytes), along with a marked improvement in the t_Zn²⁺ (from 0.348 to 0.429), enabling enhanced Zn deposition uniformity and suppressed dendrite formation. Mechanically, the electrolyte exhibited a tensile strength 27 times greater than that of standard glass fiber separators (5.5 MPa) and an 8-fold increase in puncture resistance, indicating superior structural integrity under operational stress. Notably, the cost efficiency of the skin-QSSE (183.15 m⁻²) was significantly better than that of commercial Nafion (1700 m⁻²) and GF (∼284 m⁻²), underscoring its practical viability. In full-cell configurations, the system delivered remarkable cycling durability, maintaining stable operation over 45000 cycles at a high current density of 10C, with a capacity decay rate of just 0.0018%. These findings highlight the immense potential of bioinspired, layered electrolyte architectures in overcoming key limitations of Zn–I₂ systems.

ZPBs have emerged as promising candidates for flexible and low-cost energy storage systems, but their performance is often constrained by electrolyte limitations, particularly under subzero conditions. Typically employing aqueous electrolytes such as ZnSO₄ solution, these systems benefit from high ionic conductivity and low material costs, making them suitable for ambient-temperature applications.²⁹⁶ However, at low temperatures, the aqueous nature of these electrolytes leads to crystallization and electrolyte freezing, which compromises ionic mobility and results in cell failure. Conventional antifreeze strategies, such as the incorporation of low-eutectic solvents like ethylene glycol, can effectively depress the freezing point but at the expense of increased viscosity and diminished ionic conductivity, thereby impairing charge transfer and overall electrochemical performance.²⁹⁷ Additionally, interactions between the electrolyte and polymeric electrode materials (e.g., polyaniline) may exacerbate degradation during cycling, negatively impacting cycle life and long-term stability. To address these multifaceted challenges, Pan et al.²⁶⁰ proposed a bioinspired dual-functional antifreeze electrolyte, drawing upon the antifreeze strategies of polar fish species (Fig. 26d). Mimicking the structural and functional properties of antifreeze protein–polymer complexes, a composite gel electrolyte was constructed by incorporating hemoglobin (Hb) and polyvinyl alcohol (PVA). This biomimetic electrolyte exhibited excellent flexibility, robust hydrogen-bonding networks, and enhanced low-temperature ionic transport. Uniquely, hemoglobin also acted as an electrochemical catalyst, modulating oxygen reduction kinetics in the PANI–Zn²⁺–O₂ system. DFT calculations revealed a significant increase in the O₂ binding energy with Hb (7.459 kJ mol⁻¹) and a dramatic decrease in the O₂ activation energy to −258.218 kJ mol⁻¹ (from −92.218 kJ mol⁻¹ without Hb), facilitating efficient redox reactions during cycling. This biomimetic design enabled Hb to serve as an electrocatalytic center that regulates the charge and spin state of O₂ molecules, thereby promoting electron capture, enhancing Zn²⁺ deintercalation, and enabling reversible self-charging of the PANI cathode. Electrochemical evaluations demonstrated that the battery retained stable operation at −20 °C, achieving a discharge duration of 12 minutes at 0.5C after 50 self-charging/discharging cycles, whereas the control system showed negligible capacity under identical conditions. This integrative biomimetic strategy not only achieves synergistic freezing point depression and ion conduction, but also unlocks a new avenue for developing low-temperature-adaptable, self-sustaining ZPB systems.

Although biomimetic strategies have shown considerable promise in enhancing interfacial stability, suppressing dendrite formation and mitigating dissolution and shuttle effects in emerging ZES systems, several critical challenges remain. Firstly, many current approaches are predominantly confined to morphological or structural mimicry, with limited insight into the quantitative structure–property relationships that underpin electrochemical performance. The mechanistic understanding of how specific biomimetic features influence ion transport, interfacial reactions, or degradation pathways is still underdeveloped. Secondly, most reported strategies rely on singular functional motifs and lack an integrated, multi-parameter regulatory framework. As a result, they are often insufficient to address the complex and interrelated physicochemical instabilities—such as volume changes, pH fluctuations, and by-product accumulation—that arise during extended cycling. Furthermore, the practical translation of biomimetic designs is frequently constrained by high material costs, limited scalability, and fabrication complexity.

Looking ahead, there is a pressing need to shift from superficial structural emulation toward functionally integrated and mechanism-informed design paradigms. This requires the convergence of multiscale modeling, advanced in situ/operando characterization techniques, and data-driven optimization to unravel the interplay between biomimetic architectures and electrochemical dynamics. By establishing robust design principles and performance evaluation frameworks, future research can more effectively harness biological inspiration to develop high-performance, durable, and scalable ZES devices suitable for real-world applications.

5. Zinc–ion capacitors

5.1 Bionic electrodes

ZICs have emerged as a promising energy storage technology, seamlessly bridging the high-power density of supercapacitors (SCs) with the high energy density advantages of Zn-based batteries. The theoretical foundation of SCs can be traced back over a century to the development of the electric double layer (EDL) concept (Fig. 27a).^298–302 In 1853, Hermann von Helmholtz first proposed the double-layer model, elucidating charge separation at the electrode/electrolyte interface.³⁰³ This model analogizes the EDL to a parallel-plate capacitor, where counterions in the electrolyte are electrostatically adsorbed onto the electrode surface, forming a compact Helmholtz layer. The corresponding capacitance is expressed by:

	(4)

The ε₀ represents the vacuum permittivity, ε_r is the relative permittivity of the electrolyte, A is the effective surface area of the electrode, and d denotes the separation distance between charge layers. While this classical model successfully captured the linear charge–discharge behavior of early SCs, it failed to account for the effects of ion concentration and dynamic ion distribution, paving the way for further theoretical refinements and the evolution of modern SC theory.

Building on the limitations of the Helmholtz model, significant theoretical progress was made in the early 20th century with the introduction of the diffuse double-layer (DDL) model by Gouy and Chapman.^304,305 By incorporating the effect of thermal motion on the ion distribution, this model described the EDL as comprising a compact region near the electrode and a diffuse region that extends into the electrolyte. As understanding of SC mechanisms advanced, it became evident that the finite size of solvated ions restricts their direct approach to the electrode surface. To reconcile these observations, Stern (1924) unified the Helmholtz and Gouy–Chapman models into a composite EDL theory, now known as the Gouy–Chapman–Stern (GCS) model.³⁰⁶ This framework delineates three distinct interfacial regions: the electrode surface charge layer, the compact Helmholtz layer with adsorbed counterions, and the diffuse Gouy–Chapman layer governed by ionic diffusion. By incorporating the chemisorption potential energy into the model, Stern addressed the limitations of purely electrostatic adsorption and derived the total interfacial capacitance as:

	(5)

where C denotes the areal capacitance of the entire EDL, with contributions from both the compact and diffuse layers. This model was the first to elucidate the nonlinear dependence of EDL capacitance on electrode potential: near the potential of zero charge (PZC), capacitance is primarily governed by the diffuse layer, while at higher potentials, the compact layer becomes the dominant limiting factor. The GCS model not only established a robust theoretical basis for the design of carbon-based electrodes in SCs, but also laid the groundwork for understanding the coupled “EDL-redox” synergistic mechanism that underpins high-performance ZICs.

Generally, SCs exhibit multidimensional collaborative evolution in their electrode materials. Depending on the distinct characteristics of electrode materials, conventional SCs can be categorized into four primary energy storage mechanisms: electric double-layer capacitors (EDLCs), redox pseudo-type SCs, intercalation pseudo-type SCs, and hybrid-type SCs. Among them, EDLCs (Fig. 27b) employ high surface area carbon-based materials (activated carbon, CNTs, or graphene) as active components and accomplish the energy storage at the electrode/electrolyte interface through the physical adsorption and desorption of anions and cations driven by electrostatic force. This non-faradaic process does not require electron transfer reactions, endowing EDLCs with millisecond-level response speed and ultralong cycle lifespan. However, their practical specific capacitance remains lower than the theoretical predictions due to mismatched pore structures and ion sizes. Current research focuses on designing hierarchical porous carbon materials to optimize ion transport pathways through micro-mesoporous composite channels, enhancing the effective specific surface area of carbon matrices. Nevertheless, the physical adsorption mechanism fundamentally limits energy density improvement, and the risks of electrolyte decomposition under high voltage operation. Redox pseudo-type SCs (Fig. 27c)²² achieve charge storage via surface fast Faradaic reactions in metal oxides (RuO₂ and MnO₂) or conductive polymers (polyaniline). Unlike the physical adsorption in EDLCs, this mechanism involves valence state transformations of surface atoms through redox processes. For instance, RuO₂ demonstrates reversible transitions (Ru⁴⁺ ↔ Ru³⁺) in electrolytes, each active site can store 1–3 electrons, theoretically enabling 5–10 times higher specific capacitance than EDLCs. However, practical devices still suffer from insufficient energy density due to low loading rates of active materials and sluggish proton diffusion kinetics.

Intercalation pseudo-type SCs innovatively utilize lattice gap of layered materials (MXene and MoS₂) for ion-intercalation storage (Fig. 27d). Taking MXene as an example, its 2D interlayer channels permit rapid H⁺ or Li⁺ intercalation/deintercalation during charge/discharge cycles, simultaneously preserving the high-power characteristics of EDLCs and enhancing energy density through integrated redox reactions. The critical factor for intercalation pseudo-type SCs lies in precise regulation of interlayer spacing to balance ion transport barriers and structural stability. Hybrid-type SCs achieve synergistic enhancement of energy storage mechanisms through asymmetric electrode design (Fig. 27e).¹⁰⁷ Capacitive electrodes (activated carbon) enable rapid EDL storage, and battery type electrodes provide additional capacity via ion intercalation reactions, resulting in an overall energy density close to that of LIBs.

However, the conventional SCs mentioned above still face significant limitations in energy density, safety, and cost. With the iteration of SC types, ZICs have shown high safety and high energy density, with breakthroughs in the limitations of the charge storage dimension of traditional capacitors. The breakthroughs of ZICs originate from their unique asymmetric energy storage mechanism. The cathode employs porous carbon or pseudocapacitive materials to achieve rapid ion adsorption via EDL storage or surface redox reactions. The anode utilizes the dissolution/deposition reactions of metallic Zn foil. This synergistic mechanism enables a qualitative leap in energy density while simultaneously maintaining high power density and long cycle lifespan comparable to traditional and hybrid supercapacitors. Comparatively, ZICs adopt neutral or mildly acidic aqueous electrolytes, completely eliminating flammability risks inherent in organic systems, and advanced interfacial engineering further suppresses Zn dendrite growth, enhancing operational stability. Comparative analyses reveal that ZISCs demonstrate superior performance in energy density, power density, and cost-effectiveness. Their exceptional low-temperature adaptability and intrinsic flexibility endow them with irreplaceable potential in wearable electronics and smart grid frequency regulation. Recent research advances are progressively overcoming critical bottlenecks in electrode material selection and electrolyte formulation optimization. In industrial applications, the low toxicity of Zn-based aqueous electrolytes and cost advantages of electrode materials position ZISCs as uniquely competitive candidates for large-scale energy storage.

Comparative studies have revealed that ZICs demonstrate superior performance in energy density, power density, and cost-effectiveness compared to conventional supercapacitors; their low-temperature adaptability and inherent flexibility potential make them ideal candidates for emerging applications in wearable electronics and smart grid frequency regulation. With the depth of research, ZICs are gradually breaking through the selection of electrode materials, electrolyte formulation optimization and other key technical bottlenecks. In the process of industrialization, the low-toxicity characteristics of aqueous electrolyte and the low-cost advantages of electrode materials make them show unique competitiveness in large-scale energy storage scenarios.

As a representative of the new generation of energy storage technology, ZICs are redefining the technical landscape of energy storage. Their unique dual energy storage mechanism not only breaks through the performance ceiling of traditional devices, but also opens up emerging application scenarios such as flexible electronics and micro-sensors. With the continuous progress of materials science and interface regulation technology, ZES systems are expected to become an important bridge connecting intermittent renewable energy sources and stable power output under the background of carbon neutrality, promoting the transformation of the global energy structure to a more efficient and safer direction.

To enhance the electrochemical performance of ZICs, biomimetic designs inspired by the structural and functional features of natural organisms offer significant potential. By emulating these biological principles, it is possible to advance key performance metrics such as energy density, power density, and cycling stability in ZBC systems. In the following section, several representative biomimetic strategies are highlighted to demonstrate how the structural and functional characteristics of natural organisms can be leveraged to optimize electrode materials.³¹¹ For instance, Zhang et al.³⁰⁸ drew inspiration from the porous structure of wood to fabricate a low-tortuosity hybrid aerogel thick electrode (WL-M/A-AE) with a thickness of 2000 μm using MXenes and Ag nanowires (Ag NWs) via directional freeze-drying technology (Fig. 28a). This wood-inspired porous architecture significantly improved ion transport and provided an enhanced chloride (Cl⁻) diffusion coefficient. Additionally, the incorporation of Ag NWs improved electronic conductivity, while the reversible redox reaction (Ag⁺ + Cl⁻ ↔ AgCl) facilitated Cl⁻ capture. When paired with a Zn anode, the resulting capacitor demonstrated a high area energy density of up to 292.5 μWh cm⁻², underscoring the effectiveness of bioinspired electrode engineering in enhancing ZIC performance.

Beyond plant-inspired architectures such as wood, human physiological systems have also served as powerful sources of inspiration for energy material design, particularly due to their highly evolved and efficient transport mechanisms. Among these, capillaries, as the most intricate material transport network in the human circulatory system, provide a unique model due to their multilevel bifurcated architecture and efficient mass transfer characteristics. Inspired by this biological blueprint, our group³⁰⁹ developed a capillary-inspired carbon-based nanofiber network featuring 0.86 nm channels, synthesized via a facile coordination-pyrolysis strategy (Fig. 28b). This structure was achieved by coordinating Zn²⁺ with carbonyl groups in cellulose acetate, where the Zn-coordinated regions formed robust carbon frameworks upon pyrolysis, while the uncoordinated domains decomposed to create open transport channels (CNF-Zn-800). Structural characterization confirmed precise dimensional compatibility between the capillary-like topological channels and solvated [Zn(H₂O)₆]²⁺ ion clusters, thereby mimicking the efficient “nutrient transport” behavior of biological capillaries. In situ and ex situ characterization, supported by theoretical calculations and kinetic analyses, revealed that the enhanced electrochemical performance originated from synergistic physical and chemical adsorption processes. DFT calculations highlighted the significance of pore-ion matching: conventional activated carbon with an average pore size of 0.71 nm exhibits a high ion interaction energy (E_in) of 1.01 eV due to steric incompatibility with [Zn(H₂O)₆]²⁺ clusters. In contrast, the biomimetic CNF-Zn-800 with an enlarged pore size of 1.47 nm achieved significantly lower E_in (0.33 eV), greatly reducing the energy barrier for ion transport and enabling facile access and mobility of solvated ions. The resulting electrode demonstrated ultralong cycling stability, retaining 98.7% of its initial capacity after 80000 cycles at a high current density of 10 A g⁻¹. Extending this bioinspired design strategy to the cellular level, Deng et al.³¹⁰ drew inspiration from biological ion channels embedded in cell membranes. Using a template-assisted synthesis strategy combined with crown ether molecular functionalization, bionic ion channels were constructed on the electrode surface (Fig. 28c). The strong electrostatic interaction between crown ether molecules and hydrated Zn²⁺ enabled targeted desolvation while facilitating rapid and selective ion transport. In addition, pore confinement effects further promoted the desolvation of hydrated Zn²⁺, leading to significant performance enhancement in ZICs and providing mechanistic insights into the role of chelating additives in ion regulation.

It is noteworthy that while substantial progress has been achieved in ZICs over recent years, particularly in the biomimetic design of cathode architectures and aqueous electrolyte systems, corresponding advancements in anode and separator design remain comparatively underexplored. Current research efforts predominantly center on engineering the hierarchical porosity and multiscale morphology of carbon-based cathode materials, with the aim of enhancing charge storage capacity and optimizing ion transport pathways. In contrast, the anode side continues to rely heavily on metallic Zn foil, and systematic biomimetic strategies addressing issues such as dendrite formation, interfacial instability, and surface passivation are still lacking. Similarly, although separators play a pivotal role in determining device safety, ionic conductivity, and selectivity, biomimetic design in this area is still at a nascent stage. A few studies have sought to emulate biological membrane features such as selective ion channels, self-healing capability, or mechanical compliance, attributes that could critically enhance ZIC durability and safety.

Overall, current biomimetic approaches for ZICs reveal a clear imbalance in design focus across different material components, with limited integration of multifunctional design criteria. Moving forward, the development of comprehensive biomimetic frameworks that simultaneously address anode interface regulation and separator functionality is urgently needed. This should be complemented by in situ/operando characterization techniques and theoretical modeling to elucidate the fundamental correlations between interfacial dynamics and electrochemical behavior. Such integrative strategies are expected to accelerate the realization of ZIC systems with enhanced performance, structural reliability, and scalability for practical applications.

5.2 Bionic electrolytes

To meet the practical requirements of flexible ZBCs, meticulous attention must be given to both material composition and structural design. Firstly, electrode materials must exhibit excellent electrochemical performance and mechanical flexibility to ensure stable operation under dynamic conditions such as bending and stretching. Equally critical is the selection of electrolytes, which must maintain high conductivity and stability across a wide-temperature range, enabling reliable operation in extreme environments. Inspired by the structure of fishing nets, Zheng et al.³¹² developed a gel electrolyte (PAA–PVA/PAM/Zn²⁺) by introducing polyacrylamide (PAM) and Zn²⁺ into a polyacrylic acid (PAA) and polyvinyl alcohol (PVA) matrix via in situ gelation and solvent exchange methods (Fig. 29a). This innovative design significantly enhanced the conductivity and mechanical properties of the gel electrolyte. Mimicking the mechanical robustness of fishing net, the electrolyte exhibited remarkable tensile strength, elongation, and fatigue resistance, attributed to its carefully designed structure. The assembled ZICs demonstrated excellent cycling stability over 8500 cycles at a high current density of 5 A g⁻¹ and stable performance across a wide temperature range (25 to −25 °C), highlighting their strong potential for practical applications. However, the use of organic solvents in electrolytes introduces certain safety concerns. To address these challenges, Wang et al.³¹³ developed a plant-based hydrogel electrolyte (ZPLC-PSAA), leveraging the unique properties of plant-derived components (Fig. 29b). By incorporating ZnCl₂ and harnessing its reversible interactions with plant polymers, the gel material achieved exceptional mechanical properties, anti-freezing compatibility (down to −65 °C), water retention, UV resistance, conductivity, antibacterial functionality, biocompatibility, and durable adhesion (34.8 kPa). The assembled ZICs demonstrated stable energy output across a wide temperature range, along with excellent electrochemical performance and cycle life. Furthermore, when integrated into strain sensors, the system exhibited precise and rapid monitoring of subtle deformations and vibrations in various motion states, such as finger joints, elbows, wrists, knees, and even the throat.

While plant-derived components offer sustainability and environmental compatibility, their widespread implementation in flexible energy storage devices remains limited by challenges including inconsistent raw material quality and batch-to-batch variability. To advance the scalable application of flexible supercapacitors, recent research has focused on multidimensional electrolyte regulation strategies to enhance both performance and environmental adaptability. Guo et al.³¹⁴ addressed this challenge by introducing a molecular-level electrolyte engineering approach, incorporating 1,2-propylene glycol (1,2-PG) into a polyacrylamide/zinc trifluoromethanesulfonate (Zn(CF₃SO₃)₃) hydrogel matrix (Fig. 29c). The addition of 1,2-PG disrupted the distribution of terminal groups and functional moieties within the polymer network, enabling precise reorganization of the hydrogen-bonding architecture. This restructuring reduced the mobility of free water molecules by stabilizing them through optimized hydrogen bonding, effectively suppressing water activity. DFT calculations and kinetic analyses further elucidated the benefits of this molecular-level design. The Zn²⁺ deposition activation energy in the PAM-1,2-PG electrolyte was reduced to 30.0 kJ mol⁻¹, significantly lower than that in the pristine PAM system (44.6 kJ mol⁻¹), highlighting enhanced desolvation kinetics. Moreover, the adsorption energy of 1,2-PG (−2.730 eV) was substantially more negative than that of water (−1.407 eV), enabling 1,2-PG to effectively compete with water in the solvation shell of Zn²⁺. This interaction weakens Zn²⁺–H₂O coordination, thereby reducing the desolvation energy barrier and facilitating faster ion transport. In addition to promoting ion mobility, the presence of 1,2-PG also facilitated the formation of a stable solid electrolyte interphase (SEI) layer at the electrode/electrolyte interface, effectively mitigating hydrogen evolution, dendritic growth, and other side reactions. As a result, the assembled coin cells demonstrated exceptional electrochemical performance, maintaining stable operation for over 3780 hours at −30 °C, while also demonstrating rapid charge-transfer kinetics and durable cyclability across wide-temperature ranges. This work establishes a promising direction for the development of high-performance gel electrolytes suitable for operation under extreme environmental conditions, significantly advancing the practical potential of flexible ZES systems.

The aforementioned cases demonstrate that biomimetic design in the development of ZBCs, encompassing both electrode materials and electrolytes, can effectively enhance their electrochemical performance and overall stability. By drawing inspiration from the efficient material transport and energy storage mechanisms inherent in natural systems, biomimetic approaches enable comprehensive optimization across multiple key performance parameters of ZBCs. Furthermore, biomimetic design offers a sustainable pathway for advancing energy storage technologies, promoting lower energy consumption and environmentally friendly production processes during the fabrication of ZBCs. This approach reduces reliance on traditional synthetic materials and minimizes environmental pollution associated with manufacturing. In addition, biomimetic strategies improve resource utilization efficiency and extend device lifespans, thereby mitigating resource waste and reducing electronic waste generation. As a result, biomimetic design not only drives performance improvements in ZBCs but also aligns with green energy and sustainable development goals. The dual benefits of technological innovation and environmental sustainability underscore the potential for biomimetic ZBCs to play a pivotal role in the future of energy storage. Tables 1 and 2 show the applications of biomimetic design strategies in other Zn-based batteries and capacitors, excluding ZIBs and ZABs. Through systematically introducing biological organisms high-efficiency energy conversion mechanisms, topology optimization structure, and dynamic regulation strategies into ZES device design, researchers have achieved theoretical breakthroughs and technological innovations in core issues such as electrode–electrolyte interface engineering, optimization of ion transport pathways, and device stability enhancement. The next-generation technology can deeply integrate the energy–matter synergistic transport principle at the biological system level and explore the inspiration of complex biological processes such as photosynthesis–respiration coupling and neural signal transduction networks for multi-physical field regulation in energy storage devices, and the research direction could synergize with machine learning-driven inverse design of cross-scale biomimetic structures to develop intelligent ZES systems with environmental adaptability and self-diagnostic capabilities to construct next-generation energy storage systems with enhanced safety protocols, superior energy density, and sustainable operation characteristics.

6. Challenges in the development of biomimetic technologies

6.1 Challenges in material failure

Biomimetic strategies have opened up innovative design pathways for achieving multifunctional modulation in ZES devices. By emulating structural and functional features from nature, researchers have realized notable advances in ion transport, interfacial stability, and mechanical resilience. However, despite these promising developments, challenges remain in terms of stability, adaptability, and practical feasibility under real-world operating conditions—posing critical bottlenecks for industrial translation (Fig. 30). These limitations are often underrepresented or discussed from an overly simplified perspective in the current literature, which may obscure the true industrialization potential of biomimetic approaches. This is particularly problematic for readers lacking specialized background, who may find it difficult to assess the applicability and resilience of these designs in real-world scenarios.

6.2 Challenges in scale manufacturing

While biomimetic strategies have shown considerable promise at the laboratory scale, their translation into large-scale or industrial manufacturing of ZES systems remains constrained by several critical challenges. These obstacles primarily stem from the inherent material complexity, process incompatibility, cost considerations, and a persistent mismatch between biological inspiration and engineering feasibility. Addressing these limitations will be essential for transitioning biomimetic designs from conceptual innovation to commercially viable technologies.

One major challenge lies in the complexity of fabrication. Many biomimetic structures, such as DNA-inspired supercoiled electrodes or flower-like architectures, require multistep synthesis. These include hydrothermal treatment, hard templating, atomic-level doping, and freeze-drying. Such processes are slow, energy-intensive, and hard to scale. They are often incompatible with continuous or automated manufacturing. A second barrier is the cost and sustainability of materials. Many bioinspired systems rely on rare or synthetic components such as MXenes, graphene derivatives, or advanced polymers. These materials are often expensive and not environmentally sustainable for large-scale use. A third issue is the limited functionality of current biomimetic designs. While many structures mimic biological form, they lack deeper functions like dynamic adaptation, self-healing, or selective ion transport. This gap reduces long-term stability and performance under real-world conditions. Most importantly, there is a lack of quantitative analysis regarding the industrial scalability of biomimetic systems. Most studies use coin cells for performance evaluation. However, industrial systems rely on pouch cell formats, which differ greatly in electrode area, electrolyte volume, packaging, and operating environment. As a result, lab-scale results are difficult to extrapolate to real-world systems. In addition, the field lacks a unified evaluation framework. Metrics such as unit energy cost, material utilization, and life cycle assessment are rarely reported. Without these, it is difficult to assess the feasibility of different biomimetic approaches. Future work should go beyond material design. It should also focus on scalable processing, economic feasibility, and structure–function integration. These steps are essential for moving from laboratory innovation to practical engineering applications.

7. Summary and future perspectives

7.1 Summary

Nature, as a vast repository of materials and designs, offers exceptional structural and functional characteristics that inspire innovative solutions to the challenges associated with the practical applications of ZES devices. Recognized as one of the safest and most sustainable options in the clean energy sector, ZES devices are attracting significant attention due to their low cost, environmental compatibility, and high safety. This review summarizes recent advancements in biomimetic designs inspired by the structures and functions of various plants and animals, applied to a diverse range of Zn-based energy systems, including ZIBs, ZABs, ZCBs, ZOBs, ZBBs, Zn–I₂ batteries, and ZICs. This review provides a comprehensive analysis and discussion of biomimetic strategies for optimizing different components of ZES devices, highlighting existing challenges and bridging knowledge gaps in this emerging field. By summarizing current progress and identifying critical obstacles, this review offers valuable guidance for the future development and practical application of ZES devices, advancing both technological innovation and sustainable energy solutions.

To critically assess the practical efficacy of biomimetic strategies across diverse ZES systems, we comprehensively compiled and evaluated the performance of devices featuring biomimetic designs from the extant literature. This analysis was structured according to the fundamental working mechanisms of distinct ZES systems, with consolidated data presented in Tables 1 and 2. By standardizing performance metrics under unified evaluation conditions, this comparative approach provides critical insight into the roles and advantages of specific biomimetic architectures in enhancing key parameters, notably capacity and cycling stability. Such cross-system benchmarking not only facilitates the extraction of universal biomimetic design principles but also delivers quantitative guidelines and practical benchmarks for engineering high-performance ZES devices. We anticipate that this consolidated perspective will furnish researchers with a systematic framework for rational design of bionic materials, thereby accelerating the deployment of bioinspired strategies in other advanced energy storage technologies.

To illustrate the versatility and cross-platform applicability of biomimetic strategies, Table 3 presents a comparative analysis of representative technical challenges across diverse ZES systems. For each challenge, the table maps corresponding nature-inspired design strategies, underlying biological analogues, and targeted functional improvements. This side-by-side comparison underscores the translational potential of biomimetic approaches, revealing how principles from biological systems can be systematically leveraged to address common performance bottlenecks across different ZES architectures.

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7.2 Outlook for future development

Although bioinspired strategies have demonstrated significant potential at the laboratory scale, numerous challenges remain for their practical implementation. There is an urgent need for technological innovation and interdisciplinary collaboration to advance bioinspired designs towards industrialization, intelligence, and high efficiency. Based on a thorough understanding of the current limitations, future research should focus on simplifying and scaling up material fabrication, enhancing the in-depth replication of biological functions and constructing multi-scale synergistic and dynamically adaptive systems. These efforts are essential to comprehensively improve the performance and stability of ZES devices. Addressing these challenges effectively could serve as a major driving force for the large-scale deployment and further development of ZES technologies (Fig. 31).

Author contributions

Jian Song: writing – original draft, writing – review, editing, and visualization; Qian Zhang: conceptualization, writing – review and editing; Guangjie Yang: writing – review, formal analysis; Qi Kai: writing – review, formal analysis; Xue Li: writing – review and editing; Zhenlu Liu: writing – review, visualization; Haoqi Yang: conceptualization, writing – review and editing; Ho Seok Park: methodology, writing – review and editing; Shaohua Jiang: writing – review, methodology; Jingquan Han: methodology, writing – review and editing; Shuijian He: conceptualization, methodology, writing – review and editing; Bao Yu Xia: conceptualization, methodology, writing – review and editing.

Conflicts of interest

There are no conflicts to declare.

Data availability

No primary research results, software or code have been included and no new data were generated or analyzed as part of this review.

Acknowledgements

The authors appreciate the financial support of the National Key Research and Development Program of China (no. 2021YFA1600800 and 2021YFA1501000), the National Natural Science Foundation of China (no. 22005147), the Research Plan of International Collaboration Fund for Creative Research Teams (ICFCRT) of NSFC (no. W2441008), the open research fund of Suzhou Laboratory (no. SZLAB-1308-2024-ZD010), the Yunnan Major Scientific and Technological Projects (202202AG050003), and the Innovation Capacity Construction and Enhancement Projects of Engineering Research Center of Yunnan Province (2023-XMDJ-00617107).

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