锂离子电池正极补锂技术研究进展

doi:10.19799/j.cnki.2095-4239.2024.0767

摘要/Abstract

摘要：

锂离子电池在首次充电过程中，负极表面形成固态电解质界面膜(SEI膜)的过程会不可逆地消耗电池体系中的活性锂含量，影响电池的能量密度和循环寿命，这一现象在高比能设计的电池中表现尤为明显。通过补锂技术额外补充活性锂是解决这一问题的有效手段。从工艺角度进行区分，当前补锂技术主要分为负极补锂与正极补锂，其中正极补锂技术因其安全性和电池制造工艺兼容性高而受到广泛关注。正极补锂技术主要是指在锂离子电池的正极中添加具有高不可逆容量的含锂化合物，即正极补锂添加剂/正极补锂材料。当前主流的正极补锂材料主要包含二元含锂化合物、三元含锂化合物和有机含锂化合物。此外，正极补锂也可以通过设计过嵌锂正极材料实现活性锂补偿。本文总结了当前基于正极的补锂技术与策略，综述了正极补锂技术的最新研究进展以及在提升锂离子电池首次效率、能量密度及循环寿命中的应用情况，对当前主流的正极补锂策略进行对比分析，并对未来正极补锂策略进一步实现产业化应用作出展望。

关键词: 锂离子电池, 正极补锂, 能量密度, 循环寿命

Abstract:

The formation of a solid electrolyte interface (SEI) on the surface of anodes leads to the irreversible consumption of the active lithium in lithium-ion battery systems during the first charge. This results in capacity fading and cycle life decay, particularly in the case of high-energy-density battery designs. Compensation of active lithium can be an effective way to solve such problems. The recent prelithiation strategies can be mainly divided into cathode and anode prelithiation based on the process method. Notably, cathode prelithiation technology has attracted wide attention because of its safety and high compatibility with battery-manufacturing processes. Cathode prelithiation technology mainly refers to adding lithium-containing compounds with high irreversible capacity into cathodes; in other words, cathode lithium additives are used. The main cathode lithium supplement additives are binary lithium-containing compounds, ternary lithium-containing compounds, and organic lithium-containing compounds. In addition, the active lithium replenishment of cathodes can be achieved by designing over-lithiated cathode materials. This study summarizes the research progress of cathode prelithiation strategies for improving the initial efficiency, energy density, and cycle life of lithium ion batteries. Different strategies are compared. The prospect for further commercialization of cathode prelithiation strategies is also predicted.

Key words: lithium ion batteries, cathode prelithiation, energy density, cycle life

中图分类号:

TM 911

梅悦旎, 屈雯洁, 程广玉, 向永贵, 陆海燕, 邵晓丹, 张益明, 王可. 锂离子电池正极补锂技术研究进展[J]. 储能科学与技术, 2025, 14(1): 77-89.

Yueni MEI, Wenjie QU, Guangyu CHENG, Yonggui XIANG, Haiyan LU, Xiaodan SHAO, Yiming ZHANG, Ke WANG. Recent progress of cathode prelithiation strategies for lithium ion batteries[J]. Energy Storage Science and Technology, 2025, 14(1): 77-89.

图/表 9

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图8

表1

不同正极补锂技术路线的对比"

正极补锂策略	典型代表材料	基本性质	补锂优势	存在的挑战	(潜在)应用情况
过锂化正极材料	过锂化设计的LiNi _x Co _y Mn_1-_x_-_y O₂(NCM)，LiNi_1-_x_-_y Co _x Al _y O₂(NCA)，Li₁₊_x Mn₂O₄，Li₁₊_x Mn_1.5Ni_0.5O₄等材料	通过化学或电化学方法设计制备含有过量锂的“富锂”正极材料，电池总体电化学行为不变	(1)过锂化正极材料在去锂化后，电化学体系中不残留惰性物质； (2)与NMP溶剂体系兼容性良好	(1)过锂化设计容量偏低； (2)可进行过锂化设计的正极材料种类有限； (3)过锂化正极材料的制备会额外增加生产步骤	仅适用于可进行过锂化设计的正极材料体系，但过锂化正极材料需增加额外的设计制备步骤，在规模化应用中仍存在挑战
二元含锂化合物补锂剂	LiN₃、Li₃N、Li₂O、Li₂O₂、Li₂S、Li₂Se、LiF、Li₃P等	理论补锂容量高于1000 mAh/g，金属/二元含锂化合物复合物理论补锂容量可达900 mAh/g	(1)理论补锂容量高； (2)分解产物主要为气体，成分单一	(1)完全分解电位高，与主流正极材料体系不适配，需结合改性策略降低分解电位； (2)部分材料制备时需使用熔融锂和惰性气氛，不利于规模化工业制备	结合表面包覆、基于转化反应方法等制备改性二元含锂补锂材料，同时应考虑补锂剂分解产气排出的工艺方法及引入金属单质后分解残留等问题
三元含锂化合物补锂剂	Li₂NiO₂、Li₅FeO₄、Li₆CoO₄、Li₂MoO₃、Li₈ZrO₆等	由固相反应法制备合成，补锂容量高于300 mAh/g，其中Li₅FeO₄材料理论补锂容量可达870 mAh/g	(1)制备成本较低，易于规模化生产制备； (2)分解电位区间与当前主流正极材料体系适配； (3)与NMP溶剂兼容性良好	(1)残碱高，空气稳定性及导电性较差，需结合改性方法进行改善； (2)分解后在电池体系中残留惰性金属氧化物	已实现规模化应用的正极补锂方法，综合评估最为经济实惠的补锂技术路线，适用于对于总补锂量需求不高的电化学体系
有机含锂化合物补锂剂	Li₂C₂O₄、Li₂C₄O₄、 Li₂DHBN等	由液相法合成，其中Li₂C₄O₄完全分解容量可达3845 mAh/g，具有“自牺牲”、无残留等特点	(1)制备方法简单，稳定性好，具有批量制备潜力； (2)分解电位区间与主流正极材料体系兼容	(1)本征导电性较差，需结合导电剂或催化剂的引入进行改善； (2)完全分解后产气量大，需采取后续排气措施减少产气对电池体系的不良影响	具备未来规模化应用的前景，补锂方法更加多样化，但仍面临将分解产气彻底排出电池体系等重要工艺问题

表1

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