Preparation and High Temperature Electrochemical Performance of LiNi0.08Mn1.92O4 Cathode Material of Submicron Truncated Octahedron

doi:10.6023/A21070324

Abstract

The truncated octahedral LiNi_0.08Mn_1.92O₄(LNMO) cathode material with dominant {111}, truncated {110} and {100} crystal planes was prepared by a low temperature solid-state combustion method. The dominant {111} crystal plane of the unique truncated octahedron can form firm solid electrolyte interphase (SEI) layer and alleviate the manganese dissolution during the discharge-charge process, and a small part of {110} and {100} crystal planes can increase the rapid diffusion channels of Li⁺ ions. The field emission scanning electron microscope (SEM) and X-ray diffractometer (XRD) results show that LNMO has cubic spinel structure with submicron particle size. The electrochemical performances of LNMO are also outstanding at high temperature of 55 ℃, the initial discharge capacities are 109.9 and 98.0 mAh/g with capacity retentions of 75.8% and 80.5% after 300 cycles at 1 and 5 C, respectively. Even at high current rates of 10 and 15 C, the capacity retentions of 48.4% and 49.4% have been maintained after 1000 cycles, while the capacity loss of undoped LiMn₂O₄ is as high as 98% after 1000 cycles at 15 C. Moreover, the dynamic performance tests show that LNMO owns larger Li⁺ diffusion coefficient (D=3.86×10^-15 cm²/s), smaller charge transfer resistances (before cycle and after cycles, the R_ct=158.0 and 279.8 Ω) and lower apparent activation energy (E_a=17.63 kJ/mol) than LiMn₂O₄ (LMO), demostrate its enhanced Li⁺ transport dynamic. The XRD tests of two electrode slices after 1000 cycles at 10 C show that the crystal structure of LNMO electrode material is almost unchanged, which indicated that the Ni doping and the truncated octahedral structure of particles could improve the structural stability of material, effectively inhibit the Jahn-Teller effect and Mn dissolution, remarkably improve its high temperature electrochemical performance. Therefore, this work provides a reference for the application of spinel LiMn₂O₄ electrode material at high temperature.

Key words: LiMn₂O₄, Ni doping, cathode material, high temperature electrochemical performance, truncated octahedron, solid-state combustion method, Jahn-Teller effect, Mn dissolution

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Qimei Liang, Yujiao Guo, Junming Guo, Mingwu Xiang, Xiaofang Liu, Wei Bai, Ping Ning. Preparation and High Temperature Electrochemical Performance of LiNi_0.08Mn_1.92O₄ Cathode Material of Submicron Truncated Octahedron[J]. Acta Chimica Sinica, 2021, 79(12): 1526-1533.

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Fig. & Tab. 7

Figure 1. (a) XRD patterns and (b) the enlarged (400) peaks of LMO and LNMO

Figure 2. Rietveld refinement results for XRD data of (a) LMO and (b) LNMO

Figure 3. SEM images of (a) LMO and (b) LNMO; (c, d) TEM images of LNMO

Figure 4. (a) The XPS survey and (b) the fitted curves of Mn2p3/2 of LNMO

Figure 5. Electrochemical performances of LMO and LNMO under 55 ℃: (a) rate performances at 1—15 C; (b) initial charge-discharge curves at 1 C; cycling performances at (c) 1, 5 C and (d) 10, 15 C

Figure 6. CV curves of LMO and LNMO: (a) before cycle; (b) after 1000 cycles at 10 C and 55 ℃; EIS curves of LMO and LNMO: (c) before cycle; (d) after 1000 cycles at 10 C and 55 ℃

Figure 7. XRD patterns of (a) LMO and (b) LNMO electrodes before and after 1000 cycles at 10 C and 55 ℃; (c) XPS survey and (d) the fitted curves of Mn2p3/2 of LNMO after 1000 cycles at 10 C and 55 ℃

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亚微米去顶角八面体LiNi_0.08Mn_1.92O₄正极材料制备及高温电化学性能

Preparation and High Temperature Electrochemical Performance of LiNi_0.08Mn_1.92O₄ Cathode Material of Submicron Truncated Octahedron

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亚微米去顶角八面体LiNi0.08Mn1.92O4正极材料制备及高温电化学性能