正极预锂化添加剂用于锂离子电池的研究进展

doi:10.19799/j.cnki.2095-4239.2023.0809

摘要/Abstract

摘要：

锂离子电池因其能量密度高和循环寿命长等优点，在电子产品和电动汽车等领域被广泛应用。然而，锂离子电池首次充放电过程中负极表面固态电解质界面（SEI）膜的形成会永久地消耗正极材料中的活性锂，造成不可逆的容量损失，进而降低电池首次库仑效率。已有的研究表明，预锂化技术可使电池首次库仑效率得到有效提高。在众多预锂化技术中，正极添加剂预锂化具有工艺简单、价格低廉和安全性高等优点，因此具有较为广阔的应用前景。鉴于此，本综述介绍了三类正极预锂化添加剂：三元富锂化合物、二元锂化合物和基于逆转化反应的纳米复合材料的基本工作原理和限制其发展的关键科学问题，着重归纳了近年来在预锂化添加剂材料性能优化，储能机理研究方面的研究进展和亟待解决的问题，指出了补锂添加剂在补偿首次容量损失方面的重要性，并对该方法的发展进行了展望。本文在总结当前研究进展的基础上，对正极预锂化添加剂未来的研究思路和发展方向进行了展望，提出了进一步研究预锂化添加剂的合成条件和改性策略，在不以容量牺牲为代价的前提下提升补锂添加剂的环境稳定性或开发一种新型的电解液添加剂，解决预锂化添加剂首次循环时残留物或产气对电池长循环性能的影响。这些策略有望进一步推动力离子电池的发展。

关键词: 锂离子电池, 固态电解质界面膜, 补锂技术, 正极补锂, 首次库仑效率

Abstract:

Because of its high energy density and long cycle life, Li-ion battery is widely used in electronic products and electric vehicles. However, the formation of a solid electrolyte interface (SEI) film on the anode surface during the first charge and discharge of Li-ion battery permanently consumes the active lithium in the cathode material, which results in irreversible capacity loss, and further reduces the first coulomb efficiency. The results show that prelithiation technology can effectively improve the first coulomb efficiency of the battery. Among the many prelithiation technologies, the cathode prelithiation additive has the advantages of simple process, low cost and high safety, so it has a wide application prospect. In view of this, this review describes three classes of cathode prelithiation additives: Starting from the basic working principles of ternary lithium-rich compounds, binary lithium compounds and nano composite materials based on reverse conversion reaction and the key scientific problems restricting the development of the same, the research progress and the problems to be urgently solved in the aspects of the property optimization of cathode prelithiation additive materials and energy storage mechanism research in recent years are emphatically summarized. The importance of lithium supplement additive in compensating the first capacity loss is pointed out, and the development of this method is prospected. On the basis of summarizing the current research progress, the paper forecasts the future research ideas and development direction of the cathode prelithiation additive, and puts forward the further research on the synthetic conditions and modification strategies of the prelithiation additive. improving the environmental stability of the lithium supplement additive on the premise of not sacrificing the capacity or developing a novel electrolyte additive to solve the effect of residue or gas generation on the long cycle performance of the battery when the cathode prelithiation additive is first cycled. These strategies are expected to further promote the development of power ion batteries.

Key words: lithium-ion battery, solid electrolyte interphase, pre-lithium technology, lithium cathode pre-lithiation, first coulombic efficiency

中图分类号:

TM 911

武美玲, 牛磊, 李世友, 赵冬妮. 正极预锂化添加剂用于锂离子电池的研究进展[J]. 储能科学与技术, 2024, 13(3): 759-769.

Meiling WU, Lei NIU, Shiyou LI, Dongni ZHAO. Research progress on cathode prelithium additives used in lithium-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(3): 759-769.

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Additive	Additive amount (质量分数)	Cathode	Full cell reversible capacity	Reversible capacity improvement after adding the additive	Capacity retention
Li₂NiO₂	4%	LiCoO₂	—	8%	87% after 250 cycles
Li₆CoO₄	15%	LiCoO₂	133 mAh/g	73%	约57% after 50 cycles
Li₅FeO₄	7%	LiCoO₂	144 mAh/g_LCO-LFO 156 mAh/g_LCO	14% 24%	95% after 50 cycles
Li₅FeO₄	10%	LiNi_0.5Co_0.2Mn_0.3O₂	140.8 mAh/g_LCM-LFO 154.9 mAh/g_LCM	11% 22%	98.93% after 50 cycles
Li₈ZrO₆	5%	LiNi_0.5Mn_1.5O₄	(107±3) mAh/g_LNMO-LZO (112±3) mAh/g_LNMO	10% 15%	87% after 50 cycles

Additive	Additive amount	Cathode	Chargeing platform voltage	Theroetical capacity	Capacity improvement after adding the additive
Li₂O	20%	NCM	4.5 V	1000 mAh/g	44%
Li₂O₂	2%	NCM	4.3 V	1100 mAh/g	20.5%
Li₃N	2%	LiCoO₂	0.9 V	1400 mAh/g	19%
LiN₃	—	LiMn₂O₄	4.0 V	567 mAh/g	—
LiSe	6%	LiFePO₄	3.5~4.4 V	559 mAh/g	9%
Li₃P	2.5%	LiFePO₄	2.7 V	1547 mAh/g	10.2%

Additive	Additive amount	Cathode	Chargeing platform voltage	Theroetical capacity	Capacity improvement after adding the additive
Li₂O/Co	4.8%	LiFePO₄	—	724 mAh/g	12%
Li₂O/Fe	7.5%	LiFePO₄	—	799 mAh/g	9.1%
LiF/Co	4.8%	LiFePO₄	3.2～4.2 V	520 mAh/g	20%
Li₂S/Co	4.8%	LiFePO₄	2.0 V	670 mAh/g	5.6%
Fe/LiF/Li₂O	4.8%	NCM	3.1/3.8～4.5 V	550 mAh/g	15%

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