Hybrid batteries with multiple electrochemical reactions that integrate respective advantages and remedy intricate shortages of disparate batteries are both fundamentally interesting and practically attractive. Here, an aqueous hybrid battery combining electrochemical features of Zn−Ag battery and Zn−POM battery is for the first time proposed, which is actuated by successive Ag⁺ cation and polyoxoanion redox reactions in an insoluble polyoxometalate (POM)-based cathode. The unique POM-based composite material constructed from loose stacking high-nuclearity polyoxovanadate clusters and crystalline Ag nanoparticles not only provides plentiful Zn²⁺ storage sites but also presents fast ion / electron diffusion kinetics. Meanwhile, both the severe migration of Ag⁺ ions and the dissolution of POM clusters in aqueous electrolyte are effectively inhibited. The as-fabricated hybrid battery with POM-based cathode exhibits a reversible capacity of 200 mAh g^–1 at 10 A g^–1 with outstanding capacity retention (97.4% over 7000 cycles) and superior rate capability. Moreover, the stable hybrid energy storage mechanism is revealed in detail. The work presents a promising strategy for the application of POM-based electrode in aqueous batteries and provides heuristic thinking for further developing novel energy storage systems.

具有多个电化学反应的混合电池，其综合了各自的优点并弥补了不同电池的复杂短缺，从根本上讲是很有意义的，而且在实践上很有吸引力。在此，首次提出了一种结合了Zn-Ag电池和Zn-POM电池的电化学特性的水性混合电池，该电池由不溶的多金属氧酸盐（POM）基阴极中连续的Ag ⁺阳离子和多氧阴离子氧化还原反应驱动。由松散堆积的高核聚氧钒酸盐簇和晶体Ag纳米颗粒构成的独特的基于POM的复合材料不仅提供了丰富的Zn ²⁺存储位点，而且还具有快速的离子/电子扩散动力学。同时，Ag ⁺的严重迁移离子和POM团簇在水性电解质中的溶解得到有效抑制。带有POM基阴极的混合动力电池在10 A g ^–1时具有200 mAh g ^–1的可逆容量，具有出色的容量保持能力（在7000次循环中为97.4％）和出色的倍率能力。此外，详细揭示了稳定的混合能量存储机制。这项工作为基于POM的电极在水性电池中的应用提出了一个有前途的策略，并为进一步开发新型储能系统提供了启发式思考。