Rechargeable aqueous metal-ion batteries are very promising as alternative energy storage devices during the post-lithium-ion era because of their green and safe inherent features. Among the different aqueous metal-ion batteries, aqueous zinc-ion batteries (ZIBs) have recently been studied extensively due to their unique and outstanding benefits that hold promise for large-scale power storage systems. However, zinc anode problems in ZIBs, such as zinc dendrites and side reactions, severely shorten the ZIB's cycle lifetime, thus restricting their practical application. Here, we sum up in detail the recent progress on general strategies to suppress zinc dendrites and zinc anode side reactions based on advanced materials and structure design, including the modification of the planar zinc electrode surface layer, internal structural optimization of the zinc bulk electrode, modification of the electrolyte and construction of the multifunctional separator. The various functional materials, structures and battery efficiencies are discussed. Finally, the challenges for ZIBs are identified in the production of functional zinc anodes.

Challenges in the material and structural design of zinc anode towards high-performance aqueous zinc-ion batteries

Strategies for the Stabilization of Zn Metal Anodes for Zn‐Ion Batteries

In contemporary years, the increasing demand for high-capacity and safe energy storage has spurred wide attentions in zinc batteries featuring either high voltage, high capacity or both. Despite the extensive research progress, achieving high-energy-density zinc batteries is still challenging and requires a synergy of the multiple factors including reaction mechanisms, electrodes, and electrolytes. In this Review, we comprehensively summarize the rational design strategies, and critically analyze the positive effects and potential issues in optimizing the electrochemistry, cathode materials, electrolytes and device architecture. At the end, the challenges and prospects for the further development of high-energy-density zinc batteries are outlined to guide the research towards new-generation batteries for household appliance, low-speed electric vehicles and large-scale energy storage system.

Design Strategies for High-Energy-Density Aqueous Zinc Batteries.

Layered materials have great potential as cathodes for aqueous zinc-ion batteries (AZIBs) because of their facile 2D Zn2+ transport channels; however, either low capacity or poor cycling stability limits their practical applications. Herein, two classical layered materials are innovatively combined by intercalating graphene into MoS2 gallery, which results in significantly enlarged MoS2 interlayers (from 0.62 to 1.16 nm) and enhanced hydrophilicity. The sandwich-structured MoS2 /graphene nanosheets self-assemble into a flower-like architecture that facilitates Zn-ion diffusion, promotes electrolyte infiltration, and ensures high structural stability. Therefore, this novel MoS2 /graphene nanocomposite exhibits exceptional high-rate capability (285.4 mA h g-1 at 0.05 A g-1 with 141.6 mA h g-1 at 5 A g-1 ) and long-term cycling stability (88.2% capacity retention after 1800 cycles). The superior Zn2+ migration kinetics and desirable pseudocapacitive behaviors are confirmed by electrochemical measurements and density functional theory computations. The energy storage mechanism regarding the highly reversible phase transition between 2H- and 1T-MoS2 upon Zn-ion insertion/extraction is elucidated through ex situ investigations. As a proof of concept, a flexible quasi-solid-state zinc-ion battery employing the MoS2 /graphene cathode demonstrates great stability under different bending conditions. This study paves a new direction for the design and on-going development of 2D materials as high-performance cathodes for AZIBs.

Sandwich-Like Heterostructures of MoS2/Graphene with Enlarged Interlayer Spacing and Enhanced Hydrophilicity as High-Performance Cathodes for Aqueous Zinc-Ion Batteries

Rechargeable aqueous zinc-ion batteries (AZIBs) have captured a surge of interest in recent years as a promising alternative for scalable energy storage applications owing to the intrinsic safety, affordability, environmental benignity, and impressive electrochemical performance. Despite the facilitated development of this technology by many investigations, however, its smooth implementation is still plagued by inadequate energy density and undesirable life span, which calls for an efficient and controllable cathode storage chemistry. Here, this review focuses on the key bottlenecks by offering a comprehensive summary of representative cathode materials and comparatively analyzing their structural features and electrochemical properties. Then, we critically present several feasible electrode design strategies to guide future research activities from a fundamental perspective for high-energy-density and durable cathode materials mainly in terms of interlayer regulation, defect engineering, multiple redox reactions, activated two-electron reactions, and electrochemical activation and conversion. Finally, we outline the remaining challenges and future perspectives of developing high-performance AZIBs.

Advances and Perspectives of Cathode Storage Chemistry in Aqueous Zinc-Ion Batteries.

Rechargeable zinc-ion batteries (ZIBs) are emerging as a promising alternative for Li-ion batteries. However, the developed cathodes suffer from sluggish Zn2+ diffusion kinetics, leading to poor rate capability and inadequate cycle life. Herein, an in situ polyaniline (PANI) intercalation strategy is developed to facilitate the Zn2+ (de)intercalation kinetics in V2 O5 . In this way, a remarkably enlarged interlayer distance (13.90 A) can be constructed alternatively between the VO layers, offering expediting channels for facile Zn2+ diffusion. Importantly, the electrostatic interactions between the Zn2+ and the host O2- , which is another key factor in hindering the Zn2+ diffusion kinetics, can be effectively blocked by the unique π-conjugated structure of PANI. As a result, the PANI-intercalated V2 O5 exhibits a stable and highly reversible electrochemical reaction during repetitive Zn2+ insertion and extraction, as demonstrated by in situ synchrotron X-ray diffraction and Raman studies. Further first-principles calculations clearly reveal a remarkably lowered binding energy between Zn2+ and host O2- , which explains the favorable kinetics in PANI-intercalated V2 O5 . Benefitting from the above, the overall electrochemical performance of PANI-intercalated V2 O5 electrode is remarkable improved, exhibiting excellent high rate capability of 197.1 mAh g-1 at current density of 20 A g-1 with capacity retention of 97.6% over 2000 cycles.

Tuning the Kinetics of Zinc-Ion Insertion/Extraction in V2O5 by In Situ Polyaniline Intercalation Enables Improved Aqueous Zinc-Ion Storage Performance

Developing advanced high-rate electrode materials has been a crucial aspect for next-generation lithium ion batteries (LIBs). A conventional nanoarchitecturing strategy is suggested to improve the rate performance of materials but inevitably brings about compromise in volumetric energy density, cost, safety, and so on. Here, micro-size Nb14 W3 O44 is synthesized as a durable high-rate anode material based on a facile and scalable solution combustion method. Aberration-corrected scanning transmission electron microscopy reveals the existence of open and interconnected tunnels in the highly crystalline Nb14 W3 O44 , which ensures facile Li+ diffusion even within micro-size particles. In situ high-energy synchrotron XRD and XANES combined with Raman spectroscopy and computational simulations clearly reveal a single-phase solid-solution reaction with reversible cationic redox process occurring in the NWO framework due to the low-barrier Li+ intercalation. Therefore, the micro-size Nb14 W3 O44 exhibits durable and ultrahigh rate capability, i.e., ≈130 mAh g-1 at 10 C, after 4000 cycles. Most importantly, the micro-size Nb14 W3 O44 anode proves its highest practical applicability by the fabrication of a full cell incorporating with a high-safety LiFePO4 cathode. Such a battery shows a long calendar life of over 1000 cycles and an enhanced thermal stability, which is superior than the current commercial anodes such as Li4 Ti5 O12 .

Gen Li

Papers

Tuning the Kinetics of Zinc-Ion Insertion/Extraction in V2O5 by In Situ Polyaniline Intercalation Enables Improved Aqueous Zinc-Ion Storage Performance

Achieving Ultrahigh-Rate and High-Safety Li+ Storage Based on Interconnected Tunnel Structure in Micro-Size Niobium Tungsten Oxides.