Investigation of the structural evolution and interface behavior in cathode materials for Li-ion batteries

doi:10.19799/j.cnki.2095-4239.2023.0052

Abstract

Abstract:

As a key cathode material for future high-specific capacity lithium-ion batteries, nickel-rich cathode materials have advantages of high capacity, strong stability, low cost, and environmental friendliness. Meanwhile, increasing the elemental Ni content in the materials contributes to high reversible capacity and further enhances the specific energy of the battery. However, increased nickel content in the material suffers many problems, such as increased cation mixing, which increase surface-interface side reactions, decrease thermal stability, crack crystals, and spread rapidly, as well as considerably elevate residual lithium compounds on both surface and interior of the cathode. Owing to these negative impacts, high-nickel cathode materials often suffer failure and safety problems while charging-discharging, hindering their practical applications. Based on the above considerations, we comprehensively compared and analyzed the modification methods used to stabilize and enhance the high-nickel cathode materials for Li-ion batteries in recent years. As a result, we concluded that small-scale refined structure modifications should be conducted based on the original modification strategy for developing high-nickel positive electrodes of lithium-ion batteries. Besides, the microstructure of the nickel-rich positive electrode materials should be optimized depending on their applications to improve their performance.

Key words: cathode materials, Ni-rich ternary material, stabilization, lithium-ion battery, electrochemistry

CLC Number:

O 646

Jintao LI, Yue MU, Jing WANG, Jingyi QIU, Hai MING. Investigation of the structural evolution and interface behavior in cathode materials for Li-ion batteries[J]. Energy Storage Science and Technology, 2023, 12(5): 1636-1654.

Figures/Tables 14

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Table 1

Application of concentration gradient design in recent years"

梯度策略	制备方法	应用电池类型	主要性能	文献
全浓度梯度	两股进料共沉淀法	扣式电池	保持率90%@100th(50 ℃ 5 C)	2019^[83]
梯度外壳	差分共沉淀法	扣式、袋式电池	放电容量229 mAh/g保持率88%@1000th(1 C)	2019^[77]
Ni/Mn和Al双浓度梯度	溶剂热法控制 $C O 3 2 -$ 浓度	扣式电池	保持率84.1%@400th(1.5 C) 电压衰减0.97 mV/圈(0.5 C)	2021^[84]
两级粒子双浓度梯度	共沉淀煅烧混合法	扣式、袋式电池	保持率84.1%@500th(1 C)	2022^[85]

Table 1

Fig. 8

Table 2

Table 3

Fig. 9

Fig. 10

Table 4

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掺杂离子	半径/Å	电压/V	电流密度/C	比容量/(mAh/g)		电流密度/C	循环性能		文献
				掺杂后	掺杂前		循环性能
				掺杂后	掺杂前		掺杂后	掺杂前
Mg²⁺	0.72	4.5	1	199.7	201.8	1	87.2%@200th	74%@200th	2020^[100]
Ga³⁺	0.76	4.3	0.1	246.8	233.2	0.5	90.1%@100th	68.5%@100th	2022^[116]
Zr⁴⁺	0.72	4.4	0.1	225.2	230.1	0.3	83%@100th	68%@100th	2021^[117]
F^-	1.33	—	—	—	—	0.5	96.8%@100th	60.7%@100th	2021^[87]
S^2-	1.84	4.5	0.05	270.5	261.3	0.5	81.10%@600th	65.78%@200th	2019^[118]

类型	包覆材料	电流密度/C	电压/V	容量/(mAh/g)		循环性能		文献
类型	包覆材料	电流密度/C	电压/V	包覆后	包覆前	包覆后	包覆前	文献
盐类	LiPON	0.5	4.2	174.9	176.7	97.5%@100th	94.3%@100th	2022^[131]
盐类	LiTaO₃	0.1	4.3	207.9	207.4	80.3%@150^th 60 ℃	<50%@70th 60 ℃	2022^[132]
聚合物	PEDOT	0.1	4.3	202	198	88.7%@100th	66.3%@100th	2019^[133]
聚合物	PEG+PANI	0.1	4.5	158	153	88%@100th	59%@100th	2022^[134]
氧化物	TiO₂	1	4.4	168.7	177.2	96%@200th	78%@200th	2020^[135]
氧化物	V₂O₅	0.2	4.3	210.4	196.6	83.4%@100th	71.4%@100th	2022^[122]

改性策略	改性方法	主要特点	参考文献
Ti⁴⁺掺杂全浓度梯度 Li₂ZrO₃包覆	共沉淀+不同温度煅烧+湿化学法	具有优异热稳定性和耐高压性能	2023^[146]
单晶结构 Nb²⁺梯度掺杂	喷气磨机粉碎+煅烧	高温和高电压下均具有优异稳定性和放电比容量	2022^[148]
浓度梯度 Ti⁴⁺掺杂	共沉淀+煅烧+球磨	具有高循环稳定性	2020^[149]
组分优化 La₂O₃包覆	共沉淀+研磨+煅烧	具有优异的循环稳定性和放电比容量	2022^[150]
Li₂MoO₄包覆 Mo⁶⁺掺杂	研磨+烧结	电极耐用性提升，具有高循环稳定性	2022^[151]

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