Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi0.5Mn1.5O4 spinel cathode materials

doi:10.1016/j.cjche.2023.02.020

Chinese Journal of Chemical Engineering ›› 2023, Vol. 61 ›› Issue (9): 201-209.DOI: 10.1016/j.cjche.2023.02.020

Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_0.5Mn_1.5O₄ spinel cathode materials

Jianfeng Cheng^1,2, Meixuan Li^1,2, Yutong Wang^1,2, Jiexiang Li^1,2, Jiawei Wen^1,2, Chunxia Wang^1,2, Guoyong Huang^1,2

1. College of New Energy and Materials, China University of Petroleum (Beijing), Beijing 102249, China;
2. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (Beijing), Beijing 102249, China

Received:2022-10-04 Revised:2023-02-06 Online:2023-12-14 Published:2023-09-28
Contact: Guoyong Huang,E-mail:huanggy@cup.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (52022109 and 51834008), Beijing Municipal Natural Science Foundation (2202047), National Key Research and Development Program of China (2021YFC2901100), Science Foundation of China University of Petroleum, Beijing (2462021QNX2010, 2462020YXZZ019, 2462020YXZZ016, and 2462022QZDX008).

Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_0.5Mn_1.5O₄ spinel cathode materials

Jianfeng Cheng^1,2, Meixuan Li^1,2, Yutong Wang^1,2, Jiexiang Li^1,2, Jiawei Wen^1,2, Chunxia Wang^1,2, Guoyong Huang^1,2

1. College of New Energy and Materials, China University of Petroleum (Beijing), Beijing 102249, China;
2. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (Beijing), Beijing 102249, China

通讯作者: Guoyong Huang,E-mail:huanggy@cup.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (52022109 and 51834008), Beijing Municipal Natural Science Foundation (2202047), National Key Research and Development Program of China (2021YFC2901100), Science Foundation of China University of Petroleum, Beijing (2462021QNX2010, 2462020YXZZ019, 2462020YXZZ016, and 2462022QZDX008).

Abstract

Abstract: The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_0.5Mn_1.5O₄ (LNMO) limits their further application. Herein, Al and Co were doped in LNMO materials for a more stable structure and capacity. The LNMO, LiNi_0.45Al_0.05Mn_1.5O₄ (LNAMO) and LiNi_0.45Co_0.05Mn_1.5O₄ (LNCMO) were synthesized by calcination at 900 ℃ for 8 h, which was called as solid-phase method and applied universally in industry. XRD, FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures. Moreover, the incorporation of Al and Co increased the cation disordering of LNMO, thereby increasing the transfer rate of Li⁺. The SEM results showed that the doped samples performed more regular and ortho-octahedral. The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples. Moreover, the doped samples showed better electrochemical properties than undoped LNMO. The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^-1 and 122.8 mA·h·g^-1 at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature, respectively. The capacity fading phenomenon of the doped samples at 50 ℃ and 1 C rate was significantly improved. Further, cations doping also enhanced the rate performance, especially for the LNCMO, the discharge specific capacity of 117.9 mA·h·g^-1 can be obtained at a rate of 5 C.

Key words: High voltage spinel, Al/Co doping, High temperature cycling stability

摘要： The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_0.5Mn_1.5O₄ (LNMO) limits their further application. Herein, Al and Co were doped in LNMO materials for a more stable structure and capacity. The LNMO, LiNi_0.45Al_0.05Mn_1.5O₄ (LNAMO) and LiNi_0.45Co_0.05Mn_1.5O₄ (LNCMO) were synthesized by calcination at 900 ℃ for 8 h, which was called as solid-phase method and applied universally in industry. XRD, FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures. Moreover, the incorporation of Al and Co increased the cation disordering of LNMO, thereby increasing the transfer rate of Li⁺. The SEM results showed that the doped samples performed more regular and ortho-octahedral. The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples. Moreover, the doped samples showed better electrochemical properties than undoped LNMO. The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^-1 and 122.8 mA·h·g^-1 at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature, respectively. The capacity fading phenomenon of the doped samples at 50 ℃ and 1 C rate was significantly improved. Further, cations doping also enhanced the rate performance, especially for the LNCMO, the discharge specific capacity of 117.9 mA·h·g^-1 can be obtained at a rate of 5 C.

关键词: High voltage spinel, Al/Co doping, High temperature cycling stability

Jianfeng Cheng, Meixuan Li, Yutong Wang, Jiexiang Li, Jiawei Wen, Chunxia Wang, Guoyong Huang. Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_0.5Mn_1.5O₄ spinel cathode materials[J]. Chinese Journal of Chemical Engineering, 2023, 61(9): 201-209.

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Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_0.5Mn_1.5O₄ spinel cathode materials

Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_0.5Mn_1.5O₄ spinel cathode materials

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