化工新型材料

化工新型材料 ›› 2024, Vol. 52 ›› Issue (9) : 136-142. DOI: 10.19817/j.cnki.issn1006-3536.2024.09.043

新材料与新技术

熔盐燃烧制备纳米LiN_i0.05Mn_1.95O₄正极材料及电化学性能研究

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Preparation and electrochemical properties of nano-LiN_i0.05Mn_1.95O₄ cathode materials by molten salt combustion

Ma Jiao¹, Qian Zhihui¹, Zhu Qin¹, Bai Wei¹, Guo Yujiao^1,2, Guo Junming¹

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Received
2023-06-22
Issue Date	Revised Date
2024-09-29	2023-06-22

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摘要

采用熔盐燃烧法在300℃、400℃、500℃和600℃下燃烧反应1h,然后经650℃焙烧3h,制得4种 LiN_i0.05Mn_1.95O₄正极材料。结果表明:所制LiN_i0.05Mn_1.95O₄正极材料的原有立方尖晶石结构均没有被改变,随燃烧反应温度递增,粒径略微增大,由纳米类球形颗粒变为亚微米多面体类球形颗粒。其中,燃烧反应优化温度500℃制备的LiN_i0.05Mn_1.95O₄正极材料为纳米级多面体类球形颗粒,电化学性能优良,在1C下首次放电比容量和100次充放电后容量保持率分别是103.8mAh/g和90.3%,而5C和更高倍率10C时,首次放电比容量分别为98.4mAh/g和88.2mAh/g,分别经500和1000次循环后仍有79.0%和76.1%的容量保持率。该材料具有较小的表观活化能(25.7kJ/mol)及较大的锂离子扩散系数(3.54×10^-16cm²/s)。Ni掺杂提高了循环过程中LiMn₂O₄晶体结构稳定性,抑制了Jahn-Teller畸变,适宜的燃烧反应温度可制备纳米级颗粒样品,提升其高倍率容量和电化学性能。

Abstract

Four LiN_i0.05Mn_1.95O₄ cathode materials were prepared at 300℃,400℃,500℃ and 600℃ for 1h,and then calcined at 650℃ for 3h by molten salt combustion.The results showed that the original cubic spinel structure of LiN_i0.05Mn_1.95O₄ was not changed,and the particle size increased slightly with the increase of combustion reaction temperature,transitioning from nanoscale spherical particles to submicron polyhedral spherical particles.Among them,the LiN_i0.05Mn_1.95O₄ cathode material prepared at an optimized combustion temperature of 500℃ was nanoscale polyhedral spherical particles with excellent electrochemical performance.At 1C,the first discharge specific capacity and the capacity retention ratio after 100 charge-discharge cycles were 103.8mAh/g and 90.3%,respectively.Furthermore,at 5C and higher rate of 10C,the first discharge specific capacities were 98.4 and 88.2mAh/g,respectively,and the capacity retention ratios were 79.0% and 76.1% after 500 and 1000 cycles,respectively.The material had a small apparent activation energy (25.7kJ/mol) and a large lithium-ion diffusion coefficient (3.54×10^-16cm²/s).Ni doping improved the crystal structure stability of LiMn₂O₄ during cycling and inhibited Jahn-Teller distortion.Nanoscale particle samples could be prepared at a suitable combustion reaction temperature,improving the high-rate capacity and electrochemical performance.

关键词

LiMn₂O₄ / 熔盐燃烧法 / 镍掺杂 / Jahn-Teller畸变 / 纳米尺寸 / 高倍率容量

Key words

LiMn₂O₄ / molten salt combustion method / Ni doping / Jahn-Teller effect / nanoscale / high-rate capacity

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熔盐燃烧制备纳米LiN_i0.05Mn_1.95O₄正极材料及电化学性能研究[J]. 化工新型材料, 2024, 52(9): 136-142 DOI:10.19817/j.cnki.issn1006-3536.2024.09.043

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