化工新型材料

化工新型材料 ›› 2022, Vol. 50 ›› Issue (5) : 170-175. DOI: 10.19817/j.cnki.issn1006-3536.2022.05.035

科学研究

固相燃烧法快速合成尖晶石型LiMn₂O₄正极材料及电化学性能

^1,2

^1,2*

^1,2

作者信息 +

Rapid synthesis and electrochemical property of spinel LiMn₂O₄ cathode material by solid-phase combustion

Tao Yang^1,2, Liu Xiaofang^1,2, Guo Junming^1,2, Xiang Mingwu^1,2, Bai Hongli^1,2

Author information +

文章历史 +

Received
2021-01-25
Issue Date	Revised Date
2022-06-06	2021-01-25

PDF

摘要

采用固相燃烧法在400℃、500℃、600℃和650℃一次燃烧反应1h,再在650℃焙烧6h,快速制备了LiMn₂O₄正极材料。采用X射线衍射、扫描电镜、透射电镜、X射线光电子能谱等手段对样品进行表征。结果表明:随着燃烧反应温度的升高,材料的结晶性和颗粒逐渐增大,均属于亚微米尺寸,600℃是LiMn₂O₄材料颗粒快速生长的关键温度。电化学测试表明,放电比容量和倍率性能随着燃烧温度的升高呈逐渐降低的趋势,其中燃烧温度为400℃合成的LiMn₂O₄样品(LMO-400)具有最优的倍率性能和循环寿命。在1C和5C,首次放电比容量分别为111mAh/g和90.5mAh/g,循环1000次后容量保持率分为62.1%和67.5%。EIS和CV测试结果表明,LMO-400具有较小的电荷转移电阻150Ω、较小的表观活化能22.22kJ/mol以及较大的锂离子扩散系数1.35×10^-15cm²/s。不同的燃烧反应温度对尖晶石型LiMn₂O₄颗粒尺寸、结晶性等有显著的影响,导致其电化学性能有显著差异,亚微米尺寸的颗粒具有较好的电化学性能。

Abstract

The LiMn₂O₄ cathode material was rapidly prepared by a solid-phase combustion method at 400℃,500℃,600℃ and 650℃ for 1h,and calcined at 650℃ for 6h.The as-prepared samples were characterized by XRD,SEM,TEM,XPS,etc.The results shown that with the increase of combustion reaction temperature,the crystallinity and particles of the material gradually increased,all belonging to the submicron size,and 600℃ was the key temperature for the rapid growth of LiMn₂O₄ material particles.The electrochemical test shown that the specific discharge capacity and the rate performance gradually decreased with the increase of combustion temperature.Among them,the LiMn₂O₄ sample (LMO-400) synthesized at the combustion temperature of 400℃ possessed the optimal rate performance and cycle life.At 1C and 5C,the initial specific capacity was 111mAh/g and 90.5mAh/g,respectively.After 1000 cycles,the capacity retentions were 62.1% and 67.5%.EIS and CV test results shown that the LMO-400 with the smaller charge transfer resistance of 150Ω,the smaller the apparent activation energy of 22.22kJ/mol and larger lithium ion diffusion coefficient of 1.35×10^-15cm²/s.Different combustion reaction temperatures exhibited significant effects on the size and crystallinity of spinel LiMn₂O₄ particles,resulting in significant differences in their electrochemical properties.Submicron particles presented better electrochemical properties.

关键词

燃烧反应温度 / 固相燃烧法 / LiMn₂O₄ / 正极材料 / 颗粒尺寸 / 电化学性能

Key words

combustion reaction temperature / solid-phase combustion method / LiMn₂O₄ / cathode material / particle size / electrochemical performance

引用本文

引用格式 ▾

固相燃烧法快速合成尖晶石型LiMn₂O₄正极材料及电化学性能[J]. 化工新型材料, 2022, 50(5): 170-175 DOI:10.19817/j.cnki.issn1006-3536.2022.05.035

登录浏览全文

4963

注册一个新账户忘记密码

参考文献

原文顺序 | 出版日期 | 本文引用

[1] Lee S,Yoon G,Jeong M,et al.Hierarchical surface atomic structure of a manganese-based spinel cathode for lithium-ion batteries[J].Angewandte Chemie International Edition,2015,54(4):1153-1158.
[2] Juilien C,Mangani I R,Selladurai S,et al.Synthesis,structure and electrochemistry of LiMn_2-yCr_y/2Cu_y/2O₄(0.0≤y≤0.5) prepared by wet chemistry[J].ChemInform,2002,34(1),DOI:10.1002/chin.200301021.
[3] Thirunakaran R,Sivashanmugam A,Gopukumar S,et al.Phthalic acid assisted nano-sized spinel LiMn₂O₄ and LiCr_xMn_2-xO₄(x=0.00-0.40) via sol-gel synthesis and its electrochemical behaviour for use in Li-ion-batteries[J].Materials Research Bulletin,2008,43(8-9):2119-2129.
[4] Sakunthala A,Reddy M V,Selvaskarapandian S,et al.Synthesis of compounds,Li(MMn_11/6)O₄(M=Mn_1/6,Co_1/6,(Co_1/12Cr_1/12),(Co_1/12Al_1/12),(Cr_1/12Al_1/12)) by polymer precursor method and its electrochemical performance for lithium-ion batteries[J].Electrochimica Acta,2010,55(15):4441-4450.
[5] Molenda J,Palubiak D,Marzec J.Transport and electrochemical properties of the Li_yCr_xMn_2-xO₄(0<x<0.5) cathode material[J].Journal of Power Sources,2005,144(1):176-182.
[6] 李燕,卢瑶,郭俊明,等.镧改性尖晶石LiMn₂O₄正极材料的研究进展[J].电池,2020,50(5):78-82.
[7] Wu Yu,Cao Chuanbao,Zhang Junting,et al.Hierarchical LiMn₂O₄ hollow cubes with exposed(111) planes as high-power cathodes for lithium-ion batteries[J].ACS Applied Materials & Interfaces,2016,8(30):19567-19572.
[8] Huang Sisi,Wu Hao,Chen Penghui,et al.Facile pH-mediated synthesis of morphology-tunable MnCO₃ and their transformation to truncated octahedral spinel LiMn₂O₄ cathode materials for superior lithium storage[J].Journal of Materials Chemistry A,2015,3(7):3633-3640.
[9] Kim J S,Kim K,Cho W,et al.A truncated manganese spinel cathode for excellent power and lifetime in lithium-ion batteries[J].Nano Letters,2012,12(12):6358-6365.
[10] Kuthanapillil M,Sha J,Peter G,et al.A stoichiometric nano-LiMn₂O₄ spinel electrode exhibiting high power and stable cycling[J].ChemInform,2008,20:5557-5562.
[11] 朱金玉,刘清,向明武,等.Ni-Cu双掺LiMn₂O₄正极材料的制备及电化学性能研究[J].现代化工,2020,40(12):2574-2582.
[12] Chen Kansheng,Xu Rui,Luu N S,et al.Comprehensive enhancement of nanostructured lithium-ion battery cathode materials via conformal graphene dispersion[J].Nano Letters,2017,17(4):2539-2546.
[13] Lu Jia,Zhou Cuifeng,Liu Zongwen,et al.LiMn₂O₄ cathode materials with large porous structure and radial interior channels for lithium ion batteries[J].Electrochimica Acta,2016,212:553-560.
[14] Xiang Mingwu,Su Changwei,Feng Lili,et al.Rapid synthesis of high-cycling performance LiMg_xMn_2-xO₄(x≤0.20) cathode materials by a low-temperature solid-state combustion method[J].Electrochimica Acta,2014,125:524-529.
[15] Yu Yue,Xiang Mingwu,Guo Junming,et al.Enhancing high-rate and elevated-temperature properties of Ni-Mg co-doped LiMn₂O₄ cathodes for Li-ion batteries[J].Journal of Colloid and Interface Science,2019,555:64-71.
[16] Cheng F,Wang H,Zhu Z,et al.Porous LiMn₂O₄ nanorods with durable high-rate capability for rechargeable Li-ion batteries[J].Energy & Environmental Science,2011,4(9):3668-3675.
[17] 卢瑶,白红丽,刘晓芳,等.液相无焰燃烧法制备尖晶石型LiNi_0.08Mn_1.92O₄及其电化学性能[J].电池工业,2018,22(1):21-26.
[18] 于月,向明武,白红丽,等.固相燃烧法快速合成LiNi_0.03Mg_0.10Mn_1.87O₄正极材料及电性能研究[J].稀有金属材料与工程,2020,49(4):1437-1444.
[19] 段玉珍,朱金玉,郭俊明,等.尖晶石型锰酸锂正极材料LiNi_0.01Co_0.03Mn_1.96O₄的合成及电化学性能[J].高等学校化学学报,2019,40(12):2574-2582.
[20] 罗学英,李燕,郭俊明,等.熔盐燃烧合成LiNi_0.01Cr_xMn_1.99-xO_4x(≤0.07)正极材料及电化学性能[J].高校化学工程学报,2020,34(4):1060-1068.