Research progress of high capacity Li-Mn-rich cathode materials

doi:10.19799/j.cnki.2095-4239.2022.0480

Abstract

Abstract:

Layered Li-Mn-rich materials (LMR) are promising to be next generation cathodes for lithium-ion batteries due to their high specific capacity (>250 mAh/g) and low cost. It has been nearly 30 years since the discovery of LMR material, but it has never been commercialized for the following reasons: During the cycling process, Mn³⁺ migrates into Li sites makes the layered structure transform to spinel structure, resulting in a serious discharge voltage decay, which causing serious energy loss and bringing great challenges to battery management. The low electronic conductivity of Li₂MnO₃ makes LMR material have poor rate capability and lower electrode density results in lower volume energy density of LMR. In addition, the LMR materials need to be at high voltage (>4.55 V) to show high capacity, but the electrolyte at high voltage is easy to oxidize and decompose, accompanied by the release of lattice oxygen into O₂, the above problems seriously affected LMR commercialization process. Based on the research and development results of LMR materials over the years, this paper reviews the research progress of LMR materials in the understanding of charge and discharge mechanism, precursor process route selection, modification effect and mechanism of bulk doping, surface coating, liquid and gas phase post-treatment, and the design of new special structures such as O2/O3 composite structure and single crystal structure. In addition, the future development direction and commercial prospect of LMR materials are prospected to help the industrial development of LMR materials.

Key words: Li-Mn-rich materials, charge and discharge mechanism, modification, post-treatment

CLC Number:

TM 912

Jun WANG, Xuequan ZHANG, Yafei LIU, Yanbin CHEN. Research progress of high capacity Li-Mn-rich cathode materials[J]. Energy Storage Science and Technology, 2022, 11(10): 3051-3061.

Figures/Tables 9

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Table 1

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References 36

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Modification method	LMR materials	Voltagerange	Discharge capacity/(mAh/g)	Rate capability (1 C/0.1 C)/%	Capacity retention/%	Voltage retention/%	Ref.
K⁺ doping	Li_1.151K_0.013Mn_0.552Co_0.146Ni_0.145O₂	2.0-4.8 V	315 @ 0.1 C	～73	82 (2 C, 110cyc. )	—	[10]
Ti⁴⁺ doping	Li_1.175Ti_0.025Mn_0.54Co_0.13Ni_0.13O₂	2.0-4.8 V	320 @ 0.1 C	～77	72 (0.2 C, 300cyc.)	83.6	[11]
Nb⁵⁺ doping	Li_1.2Mn_0.54Ni_0.13Co_0.13O₂	2.0-4.8 V	320 @ 0.1 C	～76	95 (0.1 C, 100cyc.)	94.7	[12]
Zr⁴⁺ doping	Li_1.2Mn_0.54Ni_0.13Co_0.13O₂	2.0-4.8 V	250 @ 0.1 C	～72	86 (1/3 C, 100cyc.)	—	[15]
AlF₃ coating	Li_1.2Ni_0.15Co_0.10Mn_0.55O₂	2.0-4.8 V	250 @ 0.1 C	—	94 (1/3 C, 130cyc.)	87.5	[23]
N-doped C coating	Li_1.2Mn_0.6Ni_0.2O₂	2.0-4.8 V	296 @ 0.1 C	～72 (5C/0.25C)	90 (1C, 500cyc.)	84.4	[36]
H₂SO₄ treatment	Li_1.143Mn_0.544Ni_0.136Co_0.136O₂	2.0-4.8 V	287 @ 0.05 C	—	99.2 (0.1 C, 50cyc.)	98.5	[30]
CO₂ treatment	Li_1.144Mn_0.544Ni_0.136Co_0.136O₂	2.0-4.8 V	301 @ 0.05 C	86.2	93.8 (0.5 C, 100cyc.)	—	[31]
O2/O3 hybrid	—	2.0-4.8 V	302 @ 0.1 C	—	93.4 (0.5 C, 100cyc.)	96.4%	[34]
Single crystal	Li_1.2Ni_0.2Mn_0.6O₂	2.0-4.8 V	230 @ 0.1 C	72.2	92 (1 C, 200cyc.)	96.5%	[35]

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