Corresponding Author

Yi HU(huyi869607143@163.com)


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 Rct 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.

Graphical Abstract


wet ball-milling, Li-ion battery, composite cathode material, LiNi 0.5Co 0.2Mn 0.3O2/LiFePO4, capacity fading mechanism

Publication Date


Online Available Date


Revised Date


Received Date



[1] Andreas K, Peter A, Margret W M. Origin of the synergetic effects of LiFe0.3Mn0.7PO4€“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 Li1.2Mn0.54-xNi0.13Co0.13ZrxO2 Cathode 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 LiNi1/3Co1/3Mn1/3O2 cathode 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. LiNi1/3Co1/3Mn1/3O2-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(Ni0.5Co0.2Mn0.3)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[NixCoyMnz]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 €œbrick 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, LiNi1/2Co1/2O2 and 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(Mn1/3Ni1/3Co1/3)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 LiNixMnyCo1-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(Ni0.5Co0.2Mn0.3)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(Ni1/3Co1/3Mn1/3)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 LiNi0.82Co0.15Al0.03O2 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 Li1.2Ni0.15Mn0.55Co0.1O2-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 LiNi0.8Mn0.1Co0.1O2 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[Ni0.5Co0.2Mn0.3]O2 and AlF3-coated Li[Ni0.5Co0.2Mn0.3]O2 blend 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 LiNi0.5Co0.2Mn0.3O2 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 LiCo1/3Ni1/3Mn1/3O2 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 LiNi0.5Co0.2Mn0.3O2 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.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.