Intelligent utilization of the anionic redox reaction (ARR) in Li-rich cathodes is an advanced strategy for the practical implementation of next-generation high-energy-density rechargeable batteries. However, due to the intrinsic complexity of ARR (e.g., nucleophilic attacks), the instability of the cathode-electrolyte interphase (CEI) on a Li-rich cathode presents more challenges than typical high-voltage cathodes. Here, we manipulate CEI interfacial engineering by introducing an all-fluorinated electrolyte and exploiting its interaction with the nucleophilic attack to construct a gradient CEI containing a pair of fluorinated layers on a Li-rich cathode, delivering enhanced interfacial stability. Negative/detrimental nucleophilic electrolyte decomposition has been efficiently evolved to further reinforce CEI fabrication, resulting in the construction of LiF-based indurated outer shield and fluorinated polymer-based flexible inner sheaths. Gradient interphase engineering dramatically improved the capacity retention of the Li-rich cathode from 43 to 71% after 800 cycles and achieved superior cycling stability in anode-free and pouch-type full cells (98.8% capacity retention, 220 cycles), respectively.

中文翻译：

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通过阴离子氧化还原实现高压和长寿命锂离子电池的梯度界面工程


富锂正极中阴离子氧化还原反应（ARR）的智能利用是下一代高能量密度可充电电池实际应用的先进策略。然而，由于ARR固有的复杂性（例如亲核攻击），富锂正极上的正极-电解质界面（CEI）的不稳定性比典型的高压正极提出了更多的挑战。在这里，我们通过引入全氟化电解质并利用其与亲核攻击的相互作用来操纵CEI界面工程，在富锂阴极上构建包含一对氟化层的梯度CEI，从而增强界面稳定性。负/有害的亲核电解质分解已得到有效发展，以进一步增强 CEI 制造，从而构建基于 LiF 的硬化外屏蔽和基于氟化聚合物的柔性内护套。梯度界面工程在 800 次循环后将富锂正极的容量保持率从 43% 显着提高到 71%，并且在无阳极和袋型全电池中分别实现了卓越的循环稳定性（98.8% 容量保持率，220 次循环）。