掺铬富锂锰基材料作为高性能全固态锂电池正极

doi:10.1016/j.actphy.2025.100200

摘要/Abstract

摘要：

具有富锂锰基材料(LRMs)的全固态锂离子电池(ASSLBs)因其高能量密度和安全性被视为下一代储能体系。然而，不可逆的氧释放导致的卤化物固态电解质(SEs)严重的界面降解问题亟待解决。本研究合成了兼具高容量与稳定性的铬掺杂LRMs材料。Cr³⁺/Cr⁶⁺的可逆氧化还原反应提升了额外的容量，同时Cr⁶⁺离子在八面体与四面体位点间的可逆迁移有效维持了材料结构稳定性。此外，强Cr–O键能稳定晶格氧，构建稳定的正极/电解质界面并缓解电压衰减。因此，采用LRMs-Cr0.1正极与卤化物电解质的ASSLBs在0.5C倍率下循环500圈，每圈容量衰减率仅为0.065%。值得注意的是，LRMs-Cr0.1//Li₂₁Si₅@Si/C全电池在0.3C倍率下循环1000圈，容量保持率接近100%，对应的能量密度为413.11 Wh kg⁻¹。该研究为开发高能量密度的固态电池提供了指导。

关键词: 全固态电池, 富锂锰基材料, 阴离子氧氧化还原, 铬掺杂, Li₂₁Si₅@Si/C阳极

Abstract:

With prospects for high energy density and safety, all-solid-state lithium-ion batteries (ASSLBs) with lithium-rich manganese-based materials (LRMs) are exploited as next-generation energy storage systems. However, the severe interfacial degradations with halide solid electrolytes (SEs) caused by the irreversible oxygen release remain to be urgently solved. In this work, we synthesized Cr-substituted LRMs with high capacity and stability. The reversible redox of Cr³⁺/Cr⁶⁺ contributes to an enhanced capacity, accompanied by the reversible migration of Cr⁶⁺ ions between octahedral and tetrahedral sites, effectively maintaining the structural stability of LRMs. Meanwhile, the strong Cr–O bond can stabilize the lattice oxygen, establish a stable cathode/electrolyte interface, and alleviate the voltage decay. Therefore, the ASSBs with LRMs-Cr0.1 cathode and halide electrolyte show an excellent cycling stability with 0.065% capacity decay per cycle for 500 cycles at 0.5C. Notably, the LRMs-Cr0.1//Li₂₁Si₅@Si/C full cell exhibits outstanding long-term cyclability over 1000 cycles with nearly 100% capacity retention at 0.3C, corresponding to an energy density of 413.11 Wh kg⁻¹. This work provides guidance for developing high energy-density solid-state batteries.

Key words: All-solid-state battery, Lithium-rich manganese-based material, Anion oxygen redox, Chromium substitution, Li₂₁Si₅@Si/C anode

高珂珂, 许浩哲, 刘兴坤, 孙春文. 掺铬富锂锰基材料作为高性能全固态锂电池正极[J]. 物理化学学报, 2026, 42(3), 100200. doi: 10.1016/j.actphy.2025.100200

Keke Gao, Haozhe Xu, Xingkun Liu, Chunwen Sun. Cr-doped lithium-rich manganese-based materials as a cathode for high-performance all-solid-state lithium batteries[J]. Acta Phys. -Chim. Sin. 2026, 42(3), 100200. doi: 10.1016/j.actphy.2025.100200

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2025.100200

https://www.whxb.pku.edu.cn/CN/Y2026/V42/I3/100200

图/表 6

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