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随着全球能源结构加速转型，开发兼具高能量密度与长循环寿命的锂离子电池已成为储能领域的重要方向。富锂锰基正极材料(LLO)因其具有高比容量(> 250 mAh g-1)和高工作电压，被认为是下一代高能量密度锂离子电池最具潜力的正极材料之一。然而，富锂锰基正极材料特殊的富锂相结构使其在循环过程中易发生晶格氧的不可逆氧化，进而引发过渡金属离子迁移、结构相变和界面副反应。同时，在全电池体系中，电极-电解质界面的反复破坏与重构等副反应会持续消耗活性锂，使LLO难以充分再锂化，进一步加剧晶格氧不稳定和副反应发生。针对上述问题，本文提出了一种基于多功能正极补锂剂Li8ZrO6(LZO)的补锂-包覆的协同改性策略，使其在全电池中同步实现原位活性锂补偿与LLO表面修饰。结果表明，LZO可以实现296.6 mAh g-1的首圈锂释放量(2.0–4.8 V)，能够有效补偿全电池中的不可逆锂损失；同时，LZO可在LLO表面形成稳定的锆基修饰层，抑制电解液分解并优化正极电解质界面(CEI)组成。与石墨负极匹配时，LZO-LLO全电池的首圈放电比容量达到218.1 mAh g-1，首圈库仑效率由58.09%提升至71.05%；在1 C下循环700圈后，容量保持率仍达62.3%。循环后形貌与表面分析进一步表明，LZO包覆层在长循环后仍能稳定存在，可有效缓解颗粒破碎，促进富LiF界面的形成，降低副反应和活性锂损耗。本研究为富锂锰基正极的实用化提供了一种简便、有效的改性思路。
Abstract：Driven by the ongoing global energy transition， the development of energy-storage devices with both high energy density and long cycle life has become a major objective in battery research. Lithium-rich manganese-based layered cathode materials (LLOs)， which deliver a high specific capacity (> 250 mAh g-1) and high operating voltage， are regarded as among the most promising cathode candidates for next-generation， high-energy-density lithium-ion batteries. However， their unique Li-rich structure promotes irreversible lattice-oxygen oxidation during cycling， which in turn triggers transition-metal migration， structural phase transition， and severe interfacial side reactions. In full-cell configurations， continuous active-lithium depletion caused by repeated breakdown and reconstruction of the electrode/electrolyte interphase further hinders complete relithiation of the cathode， thereby aggravating lattice-oxygen instability. This vicious cycle between lithium loss and lattice-oxygen degradation severely limits the practical application of LLOs. Herein， we propose a dual-functional strategy based on Li8ZrO6 (LZO) that simultaneously enables cathode prelithiation and surface coating in full-cell systems. LZO delivers a first-cycle delithiation capacity of 296.6 mAh g-1， and simultaneously forms a stable zirconium-based surface layer on LLO particles， affording a synergistic prelithiation-coating effect. When paired with a graphite anode， the LZO-LLO full cell deliver an initial discharge capacity of 218.1 mAh g-1 with an initial coulombic efficiency of 71.05%， and retains 62.3% of its capacity after 700 cycles at 1 C， whereas the unmodified counterpart becomes nearly electrochemically inactive under identical conditions. Moreover， the LZO-derived coating remains firmly adhered to the LLO surface after cycles， demonstrating excellent interfacial stability. This work provides an effective and practical route for enhancing the cycling stability of lithium-rich manganese-based cathodes and advancing their practical application.
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基本信息:
DOI：10.16026/j.cnki.iea.2026010024
中图分类号:TQ131.11;TM912
引用信息:
[1]郑程浩,孙国林,卞沛然,等.Li_(8)ZrO_(6)双功能补锂剂实现富锂锰基正极同步补锂与表面包覆[J].离子交换与吸附().DOI:10.16026/j.cnki.iea.2026010024.
基金信息:
国家重点研发计划（项目号2024YFF1401100）; 天津市自然科学基金（项目号24JCZXJC00360）; 京津冀基础研究合作专项项目（项目号B2024408025）
2026-05-20
2026-05-20
2026-05-20