Research progress on cathode prelithium additives used in lithium-ion batteries

doi:10.19799/j.cnki.2095-4239.2023.0809

Abstract

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

CLC Number:

TM 911

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.

Figures/Tables 10

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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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