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

doi:10.6023/A21070324

摘要/Abstract

采用低温固相燃烧法快速制备了一种具有{111}、{110}和{100}晶面的去顶角八面体LiNi_0.08Mn_1.92O₄(LNMO)正极材料, 其高暴露{111}晶面可以减少充放电过程中Mn的溶解, 面积相对较小的{110}和{100}晶面可增加Li⁺快速扩散的通道. 测试结果表明, 所合成的LNMO具有LiMn₂O₄特有的立方晶系结构, 其颗粒尺寸为亚微米级. LNMO的高温电化学性能优异, 在55 ℃, 1和5 C的首次放电比容量分别为109.9和98.0 mAh/g, 分别循环300次后容量保持率为75.8%和80.5%; 即使在55 ℃, 10和15 C下分别循环1000次后仍具有48.4%和49.4%的容量保持率, 而未掺杂的LiMn₂O₄于15 C循环1000次后容量损失高达98%. LNMO在55 ℃有较高的Li⁺扩散系数(D=3.86×10^-15 cm²/s)和较小的电荷转移阻抗(循环前、后R_ct=158.0和279.8 Ω)以及较低的表观活化能(E_a=17.63 kJ/mol), 说明Ni掺杂能够提高Li⁺在尖晶石型LiMn₂O₄内的扩散速率及减小锂离子在脱嵌过程中的能垒, 从而提高锂离子的扩散速率和倍率性能. 对LNMO于55 ℃循环1000次后的极片进行X射线衍射(XRD)分析, 发现LNMO电极材料的晶体结构基本保持不变, 表明Ni掺杂提高了锰酸锂材料在55 ℃长循环过程中的晶体结构稳定性, 有效抑制了Jahn-Teller效应及Mn的溶解, 显著提升了其高温电化学性能. 本工作为尖晶石LiMn₂O₄电极材料在高温方面的应用提供了借鉴.

关键词: LiMn₂O₄, Ni掺杂, 正极材料, 高温电化学性能, 去顶角八面体, 固相燃烧法, Jahn-Teller效应, Mn溶解

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

引用此文

梁其梅, 郭昱娇, 郭俊明, 向明武, 刘晓芳, 白玮, 宁平. 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[J]. 化学学报, 2021, 79(12): 1526-1533.

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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图/表 7

图1. LMO和LNMO的(a) XRD图以及(b)其(400)峰的放大图XRD

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

图2. (a) LMO和(b) LNMO的XRD精修结果

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

图3. (a) LMO和(b) LNMO的SEM照片; (c, d) LNMO的TEM照片

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

图4. LNMO样品的(a) XPS总谱图和(b) Mn2p3/2的拟合曲线

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

图5. LMO和LNMO在55 ℃下的电化学性能: (a) 在1~15 C倍率区间的倍率性能; (b) 1 C下的首次充放电曲线; (c) 1, 5 C和(d) 10, 15 C下的循环性能

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

图6. LMO和LNMO于(a) 循环前和(b) 55 ℃和10 C循环1000次后的CV曲线; LMO和LNMO于(c) 循环前和(d) 55 ℃下和10 C循环1000次后的EIS曲线

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 ℃

图7. (a) LMO和(b) LNMO样品循环前和于55 ℃和10 C循环1000次后的XRD谱图; LNMO在55 ℃和10 C循环1000次后的(c) XPS总谱图和(d) Mn2p3/2的拟合曲线

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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