新型水系锌离子电池关键技术与储能应用研究进展

Research Progress in Key Technologies and Energy Storage Applications of New Aqueous Zinc-Ion Batteries

  • 摘要: 随着可再生能源大规模并网,固定式储能对电池安全性、经济性和运行寿命提出了更高要求。水系锌离子电池具有锌资源丰富、成本较低、本征安全性较高和环境适应性较好等特点,被认为是大规模储能的潜在技术路线。然而,其发展仍受到正极结构衰变、锌负极枝晶与副反应、电解液稳定窗口受限以及实验室性能难以向实用电芯传递等问题制约。本文在梳理水系锌离子电池结构组成、储能机制和技术特性的基础上,系统总结正极结构稳定化、锌负极界面调控以及电解液与隔膜优化等关键技术,重点讨论高面载量、有限锌和有限电解液条件下的全电池性能、长期运行稳定性及大容量电芯研究进展。定量分析表明,部分体系按活性物质计算的能量密度可达119.8 W·h·kg?1,但折算至整电芯后仅为33.6 W·h·kg?1,约为前者的28%;现有1.0~2.7 A·h软包电池的体积能量密度约为68~79.5 W·h·L?1,实用条件下循环寿命多为120~390次,表明材料指标与器件性能之间仍存在明显差距。通过电解液协同调控,软包电池的日均自放电率可降低至0.13%,并在25 ℃循环900次后保持93%的容量;压力和pH原位传感的响应灵敏度分别达到137 nm·MPa?1和74.51 mV·pH?1,为大容量电芯副反应与界面异常的在线识别提供了新途径。在此基础上,本文指出水系锌离子电池后续研究应加强材料与全电池协同设计,统一循环老化与日历老化评价条件,并发展面向大容量电芯的多参数状态监测方法,从而推动材料性能向可用能量、运行寿命和储能系统可靠性有效转化。

     

    Abstract: The large-scale integration of renewable energy places increasingly stringent demands on the safety, cost, service life, and operational reliability of stationary energy-storage technologies. Aqueous zinc-ion batteries are promising candidates because zinc is abundant and inexpensive, aqueous electrolytes are intrinsically nonflammable, and cell fabrication does not require strictly anhydrous and oxygen-free environments. Their practical development, however, remains constrained by cathode structural degradation, nonuniform zinc deposition, hydrogen evolution and corrosion, the limited electrochemical stability window of aqueous electrolytes, and the incomplete transfer of laboratory-scale material performance to practical cells. This review establishes a cross-scale analytical framework that links energy-storage mechanisms, key materials, practical full-cell conditions, ampere-hour-scale cells, and operational monitoring. Recent studies are classified according to cathode stabilization, zinc-anode interfacial regulation, electrolyte solvation and additive engineering, and separator-mediated ion-transport control. Representative practical cells are then compared using cathode areal loading and areal capacity, negative-to-positive capacity ratio, electrolyte-to-capacity ratio, zinc utilization, full-cell gravimetric and volumetric energy densities, cycle life, calendar aging, and cumulative capacity throughput. Long-term behavior is further organized into an operating-stress–failure-process–quantitative-indicator hierarchy that connects cycling, standby, temperature, and dynamic-power demands with zinc corrosion, gas evolution, dendrite growth, cathode dissolution, and impedance increase, as well as capacity retention, Coulombic efficiency, energy efficiency, and rest-capacity loss. This approach distinguishes genuine materials advances from performance gains produced by excess zinc, excess electrolyte, or low active-material loading. The synthesis shows that Zn2? insertion/extraction, H? participation, multicarrier co-storage, and dissolution–deposition reactions may coexist or dominate in different cathode systems. Consequently, voltage profiles alone cannot identify the actual capacity origin, and a combined evidence chain involving phase, valence state, mass, solution species, and local interfacial environment is required. Quantitative comparison further reveals a substantial scale-dependent performance gap. A representative cell delivers 119.8 W·h·kg?1 when calculated from active materials but only 33.6 W·h·kg?1 on a full-cell basis, corresponding to approximately 28% of the material-level value. Existing 1.0–2.7 A·h pouch cells generally achieve volumetric energy densities of 68–79.5 W·h·L?1, whereas their cycle lives under relatively practical material constraints are commonly limited to 120–390 cycles. Electrolyte coordination and interfacial regulation reduce the daily self-discharge rate of a pouch cell to 0.13% and retain 93% of its capacity after 900 cycles at 25 °C. Calendar-aging studies report 96.2% capacity retention after 1000 h of intermittent resting, while representative wide-temperature systems operate from ?60 to 80 °C. These isolated results nevertheless require validation under unified material and testing boundaries. For large-format cells, in situ pressure and pH sensors provide sensitivities of 137 nm·MPa?1 and 74.51 mV·pH?1, respectively, demonstrating feasible routes for detecting gas evolution and interfacial abnormalities. The main contribution of this review is therefore not a component-by-component catalogue, but an evidence-based connection between material regulation and usable cell-level energy, lifetime, and reliability. Future research should coordinate material and full-cell design, standardize coupled cycle- and calendar-aging protocols, and develop multiparameter monitoring for ampere-hour-scale cells and small series-connected modules. These measures are essential for determining whether aqueous zinc-ion batteries can progress from laboratory demonstrations to reliable stationary energy-storage deployment.

     

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