锂离子电池正极材料LiNi 0.5Co 0.2Mn 0.3O2和LiNi 0.5Co 0.2Mn 0.3O2/LiFePO4容量衰减原因分析

doi:10.13208/j.electrochem.161229

摘要/Abstract

摘要：

采用湿法球磨法制备了锂离子电池混合正极材料LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP). 通过X射线衍射(XRD)、扫描电子显微镜(SEM)、充放电测试和电化学阻抗谱测试(EIS)等方法研究对比了LiNi _0.5Co_0.2Mn _0.3O₂(NMC532)和LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP)的容量衰减机理，结果表明：循环50次和60℃高温存储后，NMC532/LFP的容量保持率分别为97.80%、86.48%，其循环和高温存储性能较好. 循环和高温存储后NMC532和NMC532/LFP的电荷传递阻抗Rct明显增大，但NMC532/LFP的Rct较小. NMC532和NMC532/LFP的I(003)/I(104)值都有所减小，但NMC532/LFP的I(003)/I(104)值比NMC532的大，即NMC532/LFP材料的阳离子混排现象有所改善. 循环后NMC532、NMC532/LFP颗粒没有出现明显的表面开裂和链接断裂现象，但NMC532颗粒有部分发生粉化. 高温储存后NMC532颗粒表面出现裂纹，且颗粒之间的链接断裂，NMC532/LFP颗粒表面出现轻微粉化. 材料结构规整度下降，阳离子混排程度加剧，电荷传递阻抗增大是NMC532和NMC532/LFP容量衰减的主要原因.

关键词: 湿法球磨法, 锂离子电池, 混合正极材料, LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ , 容量衰减机理

Abstract: The LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP) composite cathode material for lithium-ion battery was prepared by wet ball-milling. The capacity fading behaviors of LiNi _0.5Co_0.2Mn _0.3O₂ (NMC532) and LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP) were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), charge/discharge and electrochemical impedance spectroscopy (EIS) tests. The results indicated that the capacity retention values of NMC532/LFP were 97.80% and 86.48%, respectively, after 50 cycles and 60℃ high temperature storage. The NMC532/LFP exhibited better cycle performance and high temperature storage performance. Charge transfer impedance (Rct) values increased obviously after 50 cycles and high temperature storage, in particular, the R_ct value of NMC532/LFP was smaller. The I(003)/I(104) values of NMC532 and NMC532/LFP were reduced, while that of NMC532/LFP became larger, illustrating the cation mixed phenomenon was improved. There were no apparent particle cracking and particle fracture phenomena observed after 50 cycles, however, some NMC532 powder particles were obtained. The cracks were obaerved on the surface of NMC532 particles and among particles after high temperature storage, and the slight pulverization occurred on the surface of NMC532/LFP particles. Less ordered material structure, higher degree of cation mixing and increased charge transfer resistance might be mainly responsible for the capacity fading behaviors of NMC532 and NMC532/LFP.

Key words: wet ball-milling, Li-ion battery, composite cathode material, LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ , capacity fading mechanism

中图分类号:

O646

胡燚，何湘柱, 邓忠德，孔令涌，尚伟丽. 锂离子电池正极材料LiNi _0.5Co_0.2Mn _0.3O₂和LiNi_0.5Co _0.2Mn _0.3O₂/LiFePO₄容量衰减原因分析[J]. 电化学（中英文）, 2017, 23(6): 675-683.

HU Yi HE Xiang-zhu DENG Zhong-de KONG Ling-yong SHANG Wei-li. Capacity Fading Analyses of LiNi _0.5Co_0.2Mn _0.3O₂and LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄Cathode Materials for Lithium-Ion Battery[J]. Journal of Electrochemistry, 2017, 23(6): 675-683.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.161229

https://electrochem.xmu.edu.cn/CN/Y2017/V23/I6/675

参考文献

[1] Andreas K, Peter A, Margret W M. Origin of the synergetic effects of LiFe_0.3Mn_0.7PO₄–spinel blends via dynamic in situ X-ray Diffraction measurements[J]. Journal of The Electrochemical Society,2016,163(9): A1936-A1940.

[2] Takeshi K, Norihiro K, Yo K, et al. A method of separating the capacities of layer and spinel compounds in blended cathode[J]. Journal of Power Sources,2014,245:1-6.

[3] Ren X Z(任祥忠), Liu T(刘涛), Sun L N(孙灵娜), et al. Preparation and Electrochemical Performances of Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂Cathode Materials for Lithium-Ion Batteries[J].Acta Physico-Chimica Sinica(物理化学学报),2014,30(9),1641-1649.

[4] Wang J, He X, Paillard E, et al. Lithium- and Manganese-Rich Oxide Cathode Materials for High-Energy Lithium Ion Batteries[J]. Advanced Energy Materials,2016,6:1-17.

[5] Hashem A M A, Abdel-Ghany A E, Eid A E, et al. Study of the surface modification of LiNi_1/3Co_1/3Mn_1/3O₂cathode material for lithium ion battery[J]. Journal of Power Sources,2011,196(20): 8632-8637.

[6] Rao C V, Reddy A L M, Ishikawa Y, et al. LiNi_1/3Co_1/3Mn_1/3O₂-graphene composite as a promising cathode for lithium-ion batteries[J]. ACS Applied Materials and Interfaces,2011,3(8):2966-2972.

[7] Wu K C, Wang F, Gao L L, et al. Effect of precursor and synthesis temperature on the structural and electrochemical properties of Li(Ni_0.5Co_0.2Mn_0.3)O₂[J]. Electrochimica Acta,2012,75:393-398.

[8] Xu J G, Deshpande R D, Pan J, et al. Electrode Side Reactions, Capacity Loss and Mechanical Degradation in Lithium-Ion Batteries[J]. Journal of The Electrochemical Society,2015,162(10):A2026-A2035.

[9] Noh H J, Youn S, Yoon C S, et al. Comparison of the structural and electrochemical properties of layered Li[Ni_xCo_yMn_z]O₂(x=1/3,0.5,0.6,0.7,0.8 and 0.85) cathode material for lithium ion battery[J]. Journal of Power Sources,2013,233:121-130.

[10] Fulvio P F, Veith G M, Adcock J L, et al. Fluorination of “brick and mortar” soft-templated graphitic ordered mesoporous carbons for high power lithium-ion battery[J]. Journal of Materials Chemistry A,2013(1):9414-9417.

[11] Ohzuku T, Ueda A, Nagayama Y, et al. Comparative study of LiCoO₂, LiNi_1/2Co_1/2O₂and LiNiO₂ for 4-volt secondary lithium cells[J]. Electrochimica Acta, 1993,38:1159-1167.

[12] Whitfield P S, Davidson I J, Cranswick L M D, et al. Investigation of possible superstructure and cation disorder in the lithium battery cathode materical Li(Mn_1/3Ni_1/3Co_1/3)O₂ using neutron and anomalous dispersion powder diffraction [J]. Solid State Ionics,2005,176:463-471.

[13] Padhi K A, Nanjundawamy K S, Goodenough J B. Phospho-olivine as positive electrode materials for rechargeable lithium batteries [J]. Journal of The Electrochemical Society,1997,144:1188-1194.

[14] Verma P, Maire P, Novák P. A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries[J].Electrochimica Acta,2010,55(22):6332-6341.

[15] Li X Y, Choe S Y, Joe W T. A reduced order electrochemical and thermal model for a pouch type lithium ion polymer battery with LiNi_xMn_yCo_1-x-yO₂/LiFePO₄ blended cathode[J]. Journal of Power Sources,2015,294:545-555.

[16] Nan C Y, Lu J, Li L H, et al. Size and shape control of LiFePO₄ nanocrystals for better lithium ion battery cathode materials [J]. Nano Research,2013,6(7),469-477.

[17] Zhao X, Zhuang Q C, Wu C, et al. Impedance Studies on the Capacity Fading Mechanism of Li(Ni_0.5Co_0.2Mn_0.3)O₂ Cathode with High-Voltage and High-Temperature[J]. Journal of The Electrochemical Society,2015,162(14):A2770-A2779.

[18] Li J(李佳), Xie X H(谢晓华), Xia B J(夏保佳), et al. Fading mechanisms of a graphite/Li(Ni_1/3Co_1/3Mn_1/3)O₂ cell after storage[J]. Battery Bimonthly(电池),2011,41(6):293-296.

[19] Hayashi T, Okada J, Toda E, et al. Degradation Mechanism of LiNi_0.82Co_0.15Al_0.03O₂ Positive Electrodes of a Lithium-Ion Battery by a Long-Term Cycling Test[J]. Journal of The Electrochemical Society,2014,161(6):A1007-A1011.

[20] Agubra V A, Fergus J W, Fu R J, et al. Analysis of effects of the state of charge on the formation and growth of the deposit layer on graphite electrode of pouch type lithium ion polymer batteries[J]. Journal of Power Sources,2014,270:213-220.

[21] Li Y, Bettge M, Polzin B, et al. Understanding long-term cycling performance of Li_1.2Ni_0.15Mn_0.55Co_0.1O₂-graphite lithium-ion cells[J]. Journal of The Electrochemical Society,2013,160(5):A3006-A3019.

[22] Mohanty D, Li J L, Nagpure S C, et al. Understanding the structure and structural degradation mechanisms in high-voltage, lithium-manganese-rich lithium-ion battery cathode oxides: A review of materials diagnostics[J]. MRS Energy＆Sustainability:A Review Journal,2015,16:1-24.

[23] Sun G H, Sui T, Song B H, et al. On the fragmentation of active material secondary particles in lithium ion battery cathodes induced by charge cycling[J]. Extreme Mechanics Letters,2016,9:449-458.

[24] Li J, Downie L E, Ma L, et al. Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂ Cathode Material for Lithium Ion Batteries[J]. Journal of The Electrochemical Society,2015,162(7):A1401-A1408.

[25] Song H G, Park Y J. LiLaPO₄-coated Li[Ni_0.5Co_0.2Mn_0.3]O₂and AlF₃-coated Li[Ni_0.5Co_0.2Mn_0.3]O₂blend composite for lithium ion batteries[J]. Materials Research Bulletin,2012,47:2843-2846.

[26] Zhuang Q C, Wei T, Du L L, et al. An Electrochemical Impedance Spectroscopic Study of the Electronic and Ionic Transport Properties of Spinet LiMn₂O₄[J]. J. Physical Chemistry C,2010,114(18),8614-8621.

[27] Qiu X Y, Zhuang Q C, Zhang Q Q, et al. Electrochemical and electronic properties of LiCoO₂ cathode investigated by galvanostatic cycling and EIS[J]. Phys. Chem. Chem. Phys.,2012,14(8),2617-2630.

[28] Yoshida T, Takahashi M, Morikawa S, et al. Degradation Mechanism and Life Prediction of Lithium-Ion Batteries[J]. Journal of The Electrochemical Society,2006,153(3):A576-A582.

[29] Liu W(刘文), Wang M(王苗), Chen J T(陈继涛), et al. Synthesis of LiNi_0.5Co_0.2Mn_0.3O₂ for Lithium Ion Batteries and the Mechanism of Capacity Fading at High Temperature[J]. Journal of Electrochemistry(电化学),2012,18(2):118-124.

[30] Yang Z X, Song Z L, Chu G, et al. Surface modification of LiCo_1/3Ni_1/3Mn_1/3O₂ with CoAl-MMO for lithium-ion batteries [J]. Journal of Materials Science, 2012, 47: 4205-4209.

[31] Jung S K, Gwon H, Hong J, et al. Understanding the Degradation Mechanisms of LiNi_0.5Co_0.2Mn_0.3O₂ Cathode Material in Lithium Ion Batteries[J]. Advanced Energy Materials,2014,4:1-7.

[32] Hausbrand R, Cherkashinin G, Ehrenberg H, et al. Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials:Methodology, insights and novel approaches[J]. Materials Science and Engineering B,2015,192:3-25.

[33] Wu L M, Xiao X H, Wen Y H, et al. Three-dimensional finite element study on stress generation in synchrotron X-ray tomography reconstructed nickel-manganese-cobalt based half cell[J]. Journal of Power Sources,2016,336:8-18.

锂离子电池正极材料LiNi _0.5Co_0.2Mn _0.3O₂和LiNi_0.5Co _0.2Mn _0.3O₂/LiFePO₄容量衰减原因分析

Capacity Fading Analyses of LiNi _0.5Co_0.2Mn _0.3O₂and LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄Cathode Materials for Lithium-Ion Battery

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

[1]	赵刚, 龚正良, 李益孝, 杨勇. 氧化钨和磷钨酸对LiNi_0.96Co_0.02Mn_0.02O₂材料的表面包覆改性研究[J]. 电化学（中英文）, 2023, 29(10): 2204281-.
[2]	陈思, 郑淞生, 郑雷铭, 张叶涵, 王兆林. 水热法制备锂电池Si@C负极材料的工艺优化研究[J]. 电化学（中英文）, 2022, 28(8): 2112221-.
[3]	王京玥, 王睿, 王诗琦, 王立帆, 詹纯. 一步固相法合成锂离子电池高镍层状正极材料[J]. 电化学（中英文）, 2022, 28(8): 2112131-.
[4]	谯渭川, 李芳儒, 肖瑾林, 屈丽娟, 赵晓, 张梦, 庞春雷, 李子坤, 任建国, 贺雪琴. 硅氧材料的膨胀性能研究和改善[J]. 电化学（中英文）, 2022, 28(5): 2108121-.
[5]	王加义, 郭胜楠, 王新, 谷林, 苏东. 锂离子电池高镍层状氧化物正极结构失效机制[J]. 电化学（中英文）, 2022, 28(2): 2108431-.
[6]	郭瑞琪, 吴锋, 王欣然, 白莹, 吴川. 多电子反应材料推动高能量密度电池发展：材料与体系创新[J]. 电化学（中英文）, 2022, 28(12): 2219011-.
[7]	朱振威, 邱景义, 王莉, 曹高萍, 何向明, 王京, 张浩. 人工智能在锂离子电池研发中的应用[J]. 电化学（中英文）, 2022, 28(12): 2219003-.
[8]	侯廷政, 陈翔, 蒋璐, 唐城. 当前和下一代锂离子电池电解液的原子尺度微观认识和研究进展[J]. 电化学（中英文）, 2022, 28(11): 2219007-.
[9]	李丹丹, 纪翔宇, 陈明, 杨燕茹, 王晓东, 冯光. 低聚离子液体的体相与界面及其电化学储能应用[J]. 电化学（中英文）, 2022, 28(11): 2219002-.
[10]	骆晨旭, 师晨光, 余志远, 黄令, 孙世刚. 富锂锰基层状正极材料的合成及其首周过充下的结构演化[J]. 电化学（中英文）, 2022, 28(1): 2006131-.
[11]	蔡雪凡, 孙升. 多孔电极电池的循环伏安法模拟[J]. 电化学（中英文）, 2021, 27(6): 646-657.
[12]	彭依, 张伟, 左防震, 吕浩莹, 洪凯骏. 二硒化钼纳米球储锂和储镁的性能和机理研究[J]. 电化学（中英文）, 2021, 27(4): 456-464.
[13]	周莉, 吴勰, 薛照明. 热塑性聚氨酯基聚合物电解质的制备与表征[J]. 电化学（中英文）, 2021, 27(4): 439-448.
[14]	李丽娟, 朱振东, 代娟, 王蓉蓉, 彭文. 锂离子电池正极材料Li[Ni_xCo_yMn_z]O₂ (x = 0.6, 0.85)相变对比[J]. 电化学（中英文）, 2021, 27(4): 405-412.
[15]	梁振浪, 杨耀, 李豪, 刘丽英, 施志聪. 基于不同前驱体制备的硬碳负极材料的储锂性能[J]. 电化学（中英文）, 2021, 27(2): 177-184.