Synthesis of Li3PO4-doped Li(Ni0.5Co0.2Mn0.3)O2 by rheological phase method and its electrochemical performance as cathode material for Li-ion batteries

doi:10.11949/j.issn.0438-1157.20150562

Abstract

Abstract:

LiNi_xCo_yMn_zO₂ (0＜x＜1, 0＜y＜1, 0＜z＜1) has become prosperous materials for the next generation of rechargeable lithium ion battery due to the synergistic effect of the three elements and their higher discharge voltage platform and charge-discharge capacity, but the cycle stability still need to be improved. The Ni_0.5Co_0.2Mn_0.3(OH)₂ precursor was synthesized by using the method of hydroxide co-precipitation and the lithium phosphate doped Li(Ni_0.5Co_0.2Mn_0.3)O₂powders prepared by rheological phase reaction. The crystal structure and electrochemical performance of Li₃PO₄ doped Li(Ni_0.5Co_0.2Mn_0.3)O₂powders were measured by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), galvanostatic charge-discharge, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The result indicated that Li(Ni_0.5Co_0.2Mn_0.3)O₂doped with Li₃PO₄powders maintained the laminated structure of α-type-NaFeO₂, and the spherical powders were agglomerated with primary particles around 1 μm. The initial discharge capacity of Li(Ni_0.5Co_0.2Mn_0.3)O₂powders doped with 1% (mass) Li₃PO₄ was 188.6 mA·h·g^-1 (2.2—4.6 V vs Li⁺/Li), and maintained 92.9% after 30 cycles at 0.1C. Moreover, CV results showed that oxidation and reduction potential of Li(Ni_0.5Co_0.2Mn_0.3)O₂powders doped with 1% Li₃PO₄ were 3.98 and 3.64 V, the polarization of the sample was 0.34 V. The EIS tests showed that the charge transfer resistance and Warburg resistance of Li(Ni_0.5Co_0.2Mn_0.3)O₂powders doped with 1% Li₃PO₄ were 36.7 and 0.08661 Ω. So that, Li₃PO₄ components can reduce the charge transfer resistance and Li⁺ diffusion resistance between electrode and electrolyte, and decrease the effect of polarization, thus promote the electrochemical performance of Li(Ni_0.5Co_0.2Mn_0.3)O₂.

Key words: rheological phase reaction, synthesized, Li₃PO₄, dope, Li(Ni_0.5Co_0.2Mn_0.3)O₂, cathode materials, electrochemical performance

摘要：

采用氢氧化物共沉淀法制备了锂离子电池正极材料前驱体(Ni_0.5Co_0.2Mn_0.3)(OH)₂,并用流变相反应法合成了Li₃PO₄掺杂的Li(Ni_0.5Co_0.2Mn_0.3)O₂锂离子电池正极材料。运用X射线粉末衍射和恒电流充放电对产物进行了结构和电化学性能的表征,结果表明Li₃PO₄掺杂的Li(Ni_0.5Co_0.2Mn_0.3)O₂具有标准的层状α-NaFeO₂结构,样品为1 μm左右的片状一次颗粒聚集而成的类球形二次颗粒。掺杂1%(质量分数)Li₃PO₄的Li(Ni_0.5Co_0.2Mn_0.3)O₂锂离子电池在0.1C的倍率下首次放电比容量达到188.6 mA·h·g^-1(2.2～4.6 V vs Li⁺/Li),30次循环后容量保持率为 92.9%。循环伏安、交流阻抗测试表明Li₃PO₄的掺杂可减少充放电过程中电解液和电极之间的电荷传递电阻和锂离子扩散电阻,减小极化作用,从而提升了Li(Ni_0.5Co_0.2Mn_0.3)O₂材料的电化学性能。

关键词: 流变相反应, 合成, Li₃PO₄, 掺杂, Li(Ni_0.5Co_0.2Mn_0.3)O₂, 正极材料, 电化学性能

CLC Number:

TM912.9

Zhang Rui, WU Yuanxin, HE Yunwei, AI Changchun. Synthesis of Li₃PO₄-doped Li(Ni_0.5Co_0.2Mn_0.3)O₂ by rheological phase method and its electrochemical performance as cathode material for Li-ion batteries[J]. CIESC Journal, 2015, 66(8): 3177-3182.

张睿, 吴元欣, 何云蔚, 艾常春. Li₃PO₄掺杂的Li(Ni_0.5Co_0.2Mn_0.3)O₂锂离子电池正极材料的流变相法合成及电化学性能表征[J]. 化工学报, 2015, 66(8): 3177-3182.

References 23

[1]	Armand M, Tarascon J M. Building better batteries [J]. Nature, 2008, 451 (7179): 652-657.
[2]	Terada N, Yanagi T, Arai S, et al. Development of lithium batteries for energy storage and EV applications [J]. Journal of Power Sources, 2001, 100 (1/2): 80-92.
[3]	Etacheri V, Marom R, Elazari R, et al. Challenges in the development of advanced Li-ion batteries: a review [J]. Energy & Environmental Science, 2011, 4 (9): 3243-3262.
[4]	Ellis B L, Lee Kyu Tae, Nazar L F. Positive electrode materials for Li-ion and Li-batteries [J]. Chemistry of Materials, 2010, 22 (3): 691-714.
[5]	Yabuuchi N, Ohzuku T. Novel lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for advanced lithium-ion batteries [J]. Journal of Power Sources, 2003, 119 (6): 171-174.
[6]	Koyama Y, Makimura Y, Tanaka I, et al. Systematic research on insertion materials based on superlattice models in a phase triangle of LiCoO2-LiNiO2-LiMnO2 [J]. Journal of the Electrochemical Society, 2004, 151 (9): A1499-A1506.
[7]	Jung Sung-Kyun, Gwon Hyeokjo, Hong Jihyun, et al. Understanding the degradation mechanisms of LiNi0.5Co0.2Mn0.3O2 cathode material in lithium ion batteries [J]. Advanced Energy Materials, 2014, 4 (1): 94-98.
[8]	Xiao J, Chernova N A, Upreti S, et al. Electrochemical performances of LiMnPO4 synthesized from non-stoichiometric Li/Mn ratio [J]. Phys. Chem. Chem. Phys., 2011, 13 (40): 18099-18106.
[9]	Liu Xizheng, Li Huiqiao, Yoo Eunjoo, et al. Fabrication of FePO4 layer coated LiNi1/3Co1/3Mn1/3O2: towards high-performance cathode materials for lithium ion batteries [J]. Electrochimica Acta, 2012, 83: 253-258.
[10]	Zhong Yanjun, Li Juntao, Wu Zhenguo, et al. LiMn0.5Fe0.5PO4 solid solution materials synthesized by rheological phase reaction and their excellent electrochemical performances as cathode of lithium ion battery [J]. Journal of Power Sources, 2013, 234: 217-222.
[11]	Lee M H, Kang Y J, Myung S T, et al. Synthetic optimization of Li[Ni1/3Co1/3Mn1/3]O2 via coprecipitation [J]. Electrochimica Acta, 2004, 50 (4): 939-948.
[12]	Hu Yi (胡意), Ai Changchun (艾常春), Liu Yang (刘洋), et al. Turbulent flow cycle synthesis and characterization of super-fine lithium phosphate [J]. CIESC Journal (化工学报), 2014, 65 (3): 1099-1103.
[13]	Zhao Shixi, Ding Hao, Wang Yanchao, et al. Improving rate performance of LiFePO4 cathode materials by hybrid coating of nano-Li3PO4 and carbon [J]. Journal of Alloys and Compounds,2013, 566: 206-211.
[14]	Wang Jun, Zhang Minghao, Tang Changlin, et al. Microwave-irradiation synthesis of Li1.3NixCoyMn1-x-yO2.4 cathode materials for lithium ion batteries [J]. Electrochimica Acta,2012, 80: 15-21.
[15]	Ding Yanhuai, Zhang Ping, Jiang Yong, et al. Effect of rare earth elements doping on structure and electrochemical properties of LiNi1/3Co1/3Mn1/3O2 for lithium-ion battery [J]. Solid State Ionics, 2007, 178 (13/14): 967-971.
[16]	Kong Jizhou, Yang Xiaoyan, Zhai Haifa, et al. Synthesis and electrochemical properties of Li-excess Li1+x[Ni0.5Co0.2Mn0.3]O2 cathode materials using ammonia-free chelating agent [J]. Journal of Alloys and Compounds, 2013, 580: 491-496.
[17]	Koyama Y, Tanaka I, Adachi H, et al. Crystal and electronic structures of superstructural Li1-x[Co1/3Ni1/3Mn1/3]O2 (0≤x≤1) [J]. Journal of Power Sources, 2003, 119-121: 644-648.
[18]	Kong Jizhou, Zhai Haifa, Ren Chong, et al. High-capacity Li(Ni0.5Co0.2Mn0.3)O2 lithium-ion battery cathode synthesized using a green chelating agent [J]. Journal of Solid State Electrochemistry, 2013, 18 (1): 181-188.
[19]	Liu Li, Tian Fanghua, Wang Xingyan, et al. Electrochemical behavior of spherical LiNi1/3Co1/3Mn1/3O2 as cathode material for aqueous rechargeable lithium batteries [J]. Journal of Solid State Electrochemistry, 2011, 16 (2): 491-497.
[20]	Chen Yuhong, Jiao Qishuai, Wang Liang, et al. Synthesis and characterization of Li1.05Co1/3Ni1/3Mn1/3O1.95X0.05 (X=Cl, Br) cathode materials for lithium-ion battery [J]. Comptes Rendus Chimie, 2013, 16 (9): 845-849.
[21]	Wang Fuming, Yu Menghan, Hsiao Yiju, et al. Aging effects to solid electrolyte interface (SEI) membrane formation and the performance analysis of lithium ion batteries [J]. International Journal of Electrochemical Science, 2011, 6: 1014-1026.
[22]	Sun Ke, Dillon S J. A mechanism for the improved rate capability of cathodes by lithium phosphate surficial films [J]. Electrochemistry Communications, 2011, 13 (2): 200-202.
[23]	Patil A, Patil V, Shin D W, et al. Issue and challenges facing rechargeable thin film lithium batteries [J]. Materials Research Bulletin, 2008, 43 (8/9): 1913-1942.

Synthesis of Li₃PO₄-doped Li(Ni_0.5Co_0.2Mn_0.3)O₂ by rheological phase method and its electrochemical performance as cathode material for Li-ion batteries

Li₃PO₄掺杂的Li(Ni_0.5Co_0.2Mn_0.3)O₂锂离子电池正极材料的流变相法合成及电化学性能表征

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References 23

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Kaixuan LI, Wei TAN, Manyu ZHANG, Zhihao XU, Xuyu WANG, Hongbing JI. Design of cobalt-nitrogen-carbon/activated carbon rich in zero valent cobalt active site and application of catalytic oxidation of formaldehyde [J]. CIESC Journal, 2023, 74(8): 3342-3352.
[2]	Yingxi DANG, Peng TAN, Xiaoqin LIU, Linbing SUN. Temperature swing for CO₂ capture driven by radiative cooling and solar heating [J]. CIESC Journal, 2023, 74(1): 469-478.
[3]	Yuzhe LIU, Chengcai LI, Lin LI, Shaohui WANG, Peihui LIU, Tonghua WANG. Structure-property relationship between microstructure of activated carbon and supercapacitor performance [J]. CIESC Journal, 2022, 73(4): 1807-1816.
[4]	Liubin SONG, Yixuan WANG, Yinjie KUANG, Yubo XIA, Zhongliang XIAO. Development and prospect of pivotal materials and technologies in sodium-ion batteries [J]. CIESC Journal, 2022, 73(11): 4814-4825.
[5]	Boyang REN, Xiaogang CHE, Siyu LIU, Man WANG, Xinghua HAN, Ting DONG, Juan YANG. Preparation of coal-based porous carbon nanosheets by molten salt strategy as anodes for sodium-ion batteries [J]. CIESC Journal, 2022, 73(10): 4745-4753.
[6]	Shide WU, Feng YI, Dan PING, Yifei ZHANG, Jian HAO, Guoji LIU, Shaoming FANG. NH₄Cl assisted preparation of Ni-N-CNTs catalyst and its performance for electrochemical CO₂ reduction [J]. CIESC Journal, 2022, 73(10): 4484-4497.
[7]	Shenggui MA, Bowen TIAN, Yuwei ZHOU, Lin CHEN, Xia JIANG, Tao GAO. DFT study of adsorption of H₂S on N-doped Stone-Wales defected graphene [J]. CIESC Journal, 2021, 72(9): 4496-4503.
[8]	Yuming LI, Ziye LIU, Qiyang ZHANG, Yajun WANG, Guoqing CUI, Guiyuan JIANG, Dehua HE. Preparation of nitrogen-doped carbon materials and their applications in catalysis [J]. CIESC Journal, 2021, 72(8): 3919-3932.
[9]	Chaoling HAN, Zhenqian CHEN. Effect of active carbon nanoparticles on electrochemical properties of phosphorus-nitrogen double-doped graphene [J]. CIESC Journal, 2020, 71(S1): 448-453.
[10]	Zhipeng LI, Shengli NIU, Kuihua HAN, Chunmei LU. Molecular simulation of the effect of doping modification on the adsorption properties of calcium-aluminum-based composites ester exchange catalysts [J]. CIESC Journal, 2020, 71(8): 3625-3632.
[11]	Tao HU, Xiong ZHANG, Yabin AN, Chen LI, Yanwei MA. Research progress of carbon cathode materials for Li-ion capacitors [J]. CIESC Journal, 2020, 71(6): 2530-2546.
[12]	Yating ZHANG, Bochao ZHANG, Jianlan ZHANG, Keke LI, Yongqiang DANG, Yingfeng DUAN. Research progress in “bottom-up” chemical synthesis of nanographenes [J]. CIESC Journal, 2020, 71(6): 2628-2642.
[13]	Honghui BI, Shuai JIAO, Feng WEI, Xiaojun HE. Preparation of coral-like nitrogen-doped porous carbons and its supercapacitive properties [J]. CIESC Journal, 2020, 71(6): 2880-2888.
[14]	Minghui SUN, Jingyuan CHEN, Nan XIAO, Aobo CHEN, Xuzhen WANG, Jieshan QIU. Preparation of hierarchical nitrogen-rich porous carbon from coal tar for catalytic desulfurization [J]. CIESC Journal, 2020, 71(2): 660-668.
[15]	WANG Lixia,ZHANG Zhenhua,LI Lei,ZHANG Linsen,FANG Hua,SONG Yanhua,LI Xiaofeng. Preparation and lithium storage properties of Mo₂N quantum dots@nitrogen-doped graphene composite [J]. CIESC Journal, 2020, 71(12): 5854-5862.