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[交流] 层状阴极中溶剂介导的氧化物氢化

层状阴极中溶剂介导的氧化物氢化

▲ 作者:GANG WAN, TRAVIS P. POLLARD, LIN MA, MARSHALL A. SCHROEDER, CHIA-CHIN CHEN, ZIHUA ZHU, ET AL.

▲链接:

https://www.science.org/doi/10.1126/science.adg4687

▲摘要:

自放电和化学诱导的机械效应降低了嵌入式电致变色和电化学储能装置的日历寿命和循环寿命。在可充电锂离子电池中,阴极的自放电会随着时间的推移导致电压和容量损失。主流自放电模型聚焦于锂离子从电解液扩散至阴极的过程。

研究组展示了另一种途径,其中层状过渡金属氧化物阴极的氢化通过氢从碳酸盐溶剂转移到脱锂氧化物诱导自放电。在自放电阴极中,他们进一步观察到质子和锂离子浓度梯度负相关,这有助于脱锂阴极中化学和结构的异质性,从而加速降解。

在脱锂阴极中发生的氢化会影响层状阴极的化学-机械耦合以及锂离子电池的日历寿命。

▲ Abstract:

Self-discharge and chemically induced mechanical effects degrade calendar and cycle life in intercalation-based electrochromic and electrochemical energy storage devices. In rechargeable lithium-ion batteries, self-discharge in cathodes causes voltage and capacity loss over time. The prevailing self-discharge model centers on the diffusion of lithium ions from the electrolyte into the cathode. We demonstrate an alternative pathway, where hydrogenation of layered transition metal oxide cathodes induces self-discharge through hydrogen transfer from carbonate solvents to delithiated oxides. In self-discharged cathodes, we further observe opposing proton and lithium ion concentration gradients, which contribute to chemical and structural heterogeneities within delithiated cathodes, accelerating degradation. Hydrogenation occurring in delithiated cathodes may affect the chemo-mechanical coupling of layered cathodes as well as the calendar life of lithium-ion batteries.
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