Application progress of doping technology in Mn-based lithium rich oxide cathode materials

doi:10.19799/j.cnki.2095-4239.2022.0284

Abstract

Abstract:

Because of their high energy density and high energy conversion efficiency, lithium-ion batteries (LIBs) have become the most popular energy storage device. Among the embedded cathode materials, Mn-based Li-rich oxide xLi₂MnO₃·(1-x)LiMO₂ has the highest discharge specific capacity and high working voltage; however, its poor structural stability limits its application in the field of large-scale energy storage. Based on a review of recent relevant literature, the purpose of this paper is to summarize strategies for improving the structural stability and electrochemical properties of lithium-rich cathode materials, review the structural modification design of manganese-based lithium-rich oxide cathode materials by lattice doping and analyze the effects of different doping lattice sites: lithium (Li), transition metal (TM), and oxygen (O) on their structures and properties, including single-doping and double-doping. We compare the electrochemical properties of single doping at various positions and describe structural changes in doped materials as well as the mechanism of affecting properties. According to the comprehensive analysis, the lattice-doping strategy has a significant impact on the improvement of cycle performance, rate capability, first discharge capacity, first coulomb efficiency, and voltage attenuation mitigation. Double doping has greater structural stability and better electrochemical properties than single doping. It is hoped that it will serve as an experimental foundation for the widespread use of Li-rich cathode materials in the energy storage field of next-generation high energy density LIBs.

Key words: Li-rich cathode, lattice doping, single-doping, double-doping

CLC Number:

TM 912

Ziying CHEN, Xiang DING, Qingsong TONG, Junyan LI, Jingyu HUANG. Application progress of doping technology in Mn-based lithium rich oxide cathode materials[J]. Energy Storage Science and Technology, 2022, 11(8): 2681-2690.

Figures/Tables 8

Fig. 1

Fig. 2

Table 1

Comparison of Li-rich cathode materials with different dopants (1 C=250 mAh/g)"

合成方法	材料	首次放电比容量	循环性能	倍率性能	参考文献
共沉淀	Na@0.5LiMnO₃, 0.5LiNi_1/3Co_1/3Mn_1/3O₂	286，0.1 C	223，0.2 C，100圈	185，2 C	[4]
共沉淀	Na@Li_1.23Mn_0.54 Ni_0.1Co_0.13O₂	276，0.1 C	202，1 C，100圈	125，5 C	[18]
溶胶凝胶	1%Na@Li_1.2Mn_0.54 Ni_0.13Co_0.13O₂	227，0.1 C	85%，10 C，1000圈	112，10 C	[19]
溶胶凝胶	5% Cs@Li_1.23Mn_0.54 Ni_0.1Co_0.13O₂	280，0.1 C	195，0.5 C，100圈	116，10 C	[20]
水热	5%K@Li₂MoO₃	235，0.064 C	56%，0.064 C，100圈	83，2.56 C	[21]
水热	(900 ℃)K@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	315，0.08 C	267，1.6 C，110圈	—	[5]
共沉淀	K@LiNi_0.5Co_0.2Mn_0.3O₂	176.5，0.11 C	148，1.11 C，100圈	100，5.54 C	[22]
共沉淀	2.5%Rb@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	221.9，0.2 C	92.78%，0.2 C，100圈	117.6，2 C	[6]
—	2.5%Mg@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	250，0.08 C	195，0.08 C，100圈	120，4 C	[7]
溶胶凝胶	1%Mg@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	304	210，0.1 C，100圈	—	[23]
溶胶凝胶	2%Mg@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	275.8，0.16 C	254.9，0.16 C，50圈	127.5，4 C	[24]
溶胶凝胶	0.4%Ca@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	246，0.2 C	87%，0.2 C，100圈	133，4 C	[8]
溶剂热	3%Al@Li_1.5Mn_0.675Ni_0.1675Co_0.1675O₂	323.7，0.1 C	200，0.5 C，150圈	120，20 C	[25]
溶胶凝胶	2.5%Ti@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	320，0.24 C	229，0.24 C，300圈	136，6 C	[10]
共沉淀	8%Mg@Li_1.17Ni_0.25-_x Mn_0.58Mg _x O₂	201	95.1%，2 C，100圈	104.4，5 C	[26]
共沉淀	1%Mg@Li_1.2Ni_0.2Mn_0.6O₂	140.6，0.04 C	226.5，0.08 C，60圈	212.7，0.08 C	[27]
共沉淀	4%Mg@Li_1.2Ni_0.12Co_0.12Mn_0.56O₂	217.8，0.05 C	236.9，30圈	176.5，1.0 C	[28]
—	9%Mg@Li_1.2Ni_0.16Mn_0.56Co_0.08O₂	160，0.1 C	210，0.1 C，100圈	120，4 C	[29]
溶胶凝胶	4%Al@Li_1.14(Ni_0.136Co_0.136Mn_0.544)O₂	212，0.08 C	94.65%，100圈	—	[11]
共沉淀	Cr@Li(Li_0.2Mn_0.54Ni_0.13Co_0.13)O₂	219，0.05 C	170，0.2 C，133圈	—	[30]
高温固相	0.3%Cu@Li_1.05FePO₄	145	85%，40圈	75，3 C	[31]
共沉淀	Ga@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	259.8，0.05 C	229.4，0.1 C，100圈	155.7，5 C	[32]
共沉淀	2.5%Nb@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	282.6，0.05 C	83%，1 C，100圈	173.1，2 C	[33]
共沉淀	17.5%Se@Li_1.2Mn_0.56Ni_0.16Co_0.08O₂	265，0.08 C	93%，0.08 C，100圈	178，8 C	[34]
高温固相	Li_1.2Mn_0.568Ni_0.2Sn_0.032O₂	225，0.02 C	125，0.4 C，100圈	123，0.4 C	[9]
固相热解	2%V@Li_1.2Mn_0.52Co_0.08Ni_0.2O₂	253，0.1 C	152.2，1 C，50圈	99，5 C	[35]
热聚合	2%Mo@Li_1.2Ni_0.2Mn_0.6O₂	235，0.1	229，0.1 C，204圈	110，5 C	[36]
共沉淀	S@Li_1.2Mn_0.6Ni_0.2O₂	293.3，0.1 C	213.4，0.1 C，67圈	190，2 C	[37]
高温固相	0.6%B@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	293.9，0.4 C	228.55，0.4 C，100圈	—	[13]
高温固相	0.5%B@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	—	211，0.2 C，50圈	—	[38]
溶胶凝胶	B@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	—	190，0.2 C，100圈	—	[14]
共沉淀	2.5%F@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	200，0.2 C	87%，0.2 C，100圈	—	[12]
高温固相	2.5%F@Li(Li_1/6Ni_1/6Co_1/6Mn_1/2)O₂	275，0.1 C	198.75，1 C，40圈	—	[39]

Table 1

Fig. 3

Fig. 4

Fig. 5

Fig. 6

Fig. 7

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