Research Progress on the Degradation Mechanism and Cycle Stability Improvement of Lithium-Rich Cathode Materials

doi:10.19894/j.issn.1000-0518.210059

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (02): 205-222.DOI: 10.19894/j.issn.1000-0518.210059

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Research Progress on the Degradation Mechanism and Cycle Stability Improvement of Lithium-Rich Cathode Materials

Ying ZHAO¹, Yi-Jia SHAO¹, Luo-Qian LI¹, Jian-Wei REN²(), Shi-Jun LIAO¹()

^1.The Key Laboratory of Fuel Cells Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, China
^2.Department of Mechanical Engineering Science, University of Johannesburg, Johannesburg ZA-2092, South Africa

Received:2021-02-02 Accepted:2021-06-09 Published:2022-02-10 Online:2022-02-09
Contact: Jian-Wei REN,Shi-Jun LIAO
Supported by:
National Key Research and Development Program of China(2017YFB0102900);National Natural Science Foundation of China(51971094);Guangdong Provincial Department of Science and Technology(2015A030312007)

Abstract

Abstract:

The lithium-rich cathode material xLi₂MnO₃· (1-x) LiMO₂ (M=Ni, Co, Mn, etc., 0<x<1) has the huge advantages of high capacity (up to 300 mA·h/g or more) and low cost, and is known as probably the most important next-generation cathode material for lithium-ion batteries. It has received great attention and extensive research from various countries. At present, this material still has problems such as low initial (first cycle) Coulomb efficiency, poor cycle performance, and serious voltage attenuation, which all seriously hinder the development and practical application of the material. In order to solve these problems of this material, especially its insufficient cycle stability and voltage attenuation, a lot of research work has been carried out on the degradation mechanism and stability improvement of the lithium-rich cathode material, and some important progresses have been made in recent years. This article introduces the structure and working principle of the lithium-rich cathode material, focusing on the research work in recent years on the degradation mechanism of the lithium-rich cathode material and improving the stability of the lithium-rich cathode material. The further research work has been prospected.

Key words: Lithium-ion battery, Lithium-rich cathode material, Degradation mechanism, Stability improvement, Bulk phase doping, Surface coating

CLC Number:

O646

Ying ZHAO, Yi-Jia SHAO, Luo-Qian LI, Jian-Wei REN, Shi-Jun LIAO. Research Progress on the Degradation Mechanism and Cycle Stability Improvement of Lithium-Rich Cathode Materials[J]. Chinese Journal of Applied Chemistry, 2022, 39(02): 205-222.

Figures/Tables 15

Fig.1 Crystal structure diagram of（a）LiMO2，（b）Li2MnO3and（c）Li-rich materials［32］

Fig.2 Image of Li1.2Co0.1Mn0.55Ni0.15O2observed by high resolution transmission electron microscope（HR-TEM）［37］

Fig.3 The first charge-discharge curves of lithium-rich layered cathode materials［45］

Fig.4 （a）Honeycomb-type cation arrangement in the TM layer of Li1.2Ni0.13Co0.13Mn0.54O2；（b）Oxygen in the honeycomb structure coordinated by Mn4+and Li+；（c）O－／O2－Energy and state density diagram［47］

Fig.5 Figures of the fitting results of PDF spectra at different states of OCV，pristine，charged to 4.4 V，and charged to 4.8 V（left）；Figures of the local structure around the center Mn atom. Purple：Mn，red：O（right）［49］

Fig.6 Diagram of phase transition sequence and structural degradation of the Li-rich cathode materials［53］

Fig.7 （a）Rate performance of LNCM and LNCM-K；Cycling performance of LNCM and LNCM-K at（b）0.5 C，（c）5 C and 10 C［59］

Fig.8 Cycling performance of LNCM and LNCM-Pt at（a）0.5 C，（b）1 C and（c）2 C［71］

Fig.9 （a）First charge-discharge characteristics of NM-LRM and PD-LRM at 0.1 C；（b）Rate performance of NM-LRM and PD-LRM；（c）Cycle performance of NM-LRM and PD-LRM at 1 C［79］

Fig.10 （a）First charge-discharge characteristics of LMNC，Na-LMNC，F-LMNC，and NaF-LMNC at 0.1 C；（b）Rate performance of LMNC，Na-LMNC，F-LMNC，and NaF-LMNC；（c）Cycle performance of LMNC，Na-LMNC，F-LMNC，and NaF-LMNC at 1 C；（d）Voltage fading of LMNC，Na-LMNC，F-LMNC，and NaF-LMNC［86］

Fig.11 （a）Rate performance of M0 and M1；（b）Cycling performance of M0 and M1 at（b）0.5 C，（c）2 C；（d）Discharge median voltage of M0 and M1 at 1 C［89］

Fig.12 （a）First charge-discharge characteristics of materials before and after modification at 0.1 C；（b）Cycling performance of materials before and after modification at 1 C；（c）Rate performance of materials before and after modification at 0.1 C［104］

Fig.13 （a）Cycling performance of LMNCO@RGO and LMNCO NTs at 1 C；（b）Rate performance of LMNCO@RGO and LMNCO NTs［114］

Fig.14 （a）First charge-discharge performance of materials before and after modification at 0.1 C；（b）rate performance of materials before and after modification；cycling performance of materials before and after modification at（c）1 C，（d）5 C［120］

Fig.15 （a）first charge-discharge performance of LLO@MDZ and LLO at 0.1 C；（b）Rate performance of LLO@MDZ and LLO；（c）Cycling performance and coulombic efficiency of LLO@MDZ at 1 C；（d）Cycling performance and coulombic efficiency of LLO at 1 C［131］

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Research Progress on the Degradation Mechanism and Cycle Stability Improvement of Lithium-Rich Cathode Materials

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