Li_3VO_4修饰富镍LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2正极材料的电化学性能
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摘要
采用湿法融合技术及高温固相法合成Li_3VO_4包覆的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2正极材料。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等方法研究材料的结晶相、形貌、微观结构。研究表明,Li_3VO_4均匀地包覆在Li Ni0.8Co0.1Mn0.1O_2表面,未改变原材料的材料结构和形貌,包覆层厚度为1～2 nm。不同含量的Li_3VO_4对LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2正极材料进行修饰研究表明,3%(质量)Li_3VO_4包覆的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2在1 C下100次循环后容量保持率为94.13%,具有最佳的倍率性能和循环性能。此外,循环伏安(CV)和交流阻抗(EIS)分析表明,Li_3VO_4能提高Li+电导率,抑制活性材料与电解液之间的副反应,提高材料的电化学性能。
The Li_3VO_4 coated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2 cathode material was synthesized by wet fusion technology and high temperature solid phase method. The crystalline phase, morphology and microstructure of materials were studied by X-ray diffraction(XRD), scanning electron microscope(SEM) and transmission electron microscope(TEM). The results show that Li_3VO_4 is evenly coated on the surface of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2 without changing the material structure and morphology of the raw materials. The coating thickness is 1—2 nm. The modification of Li Ni0.8 Co0.1 Mn0.1 O_2 cathode material with different content of Li_3VO_4 shows that 3%(mass) Li_3VO_4 coated Li Ni0.8 Co0.1 Mn0.1 O_2 has a capacity retention rate of 94.13% after 100 cycles under 1 C, which has the best multiplier performance and cycling performance. In addition, cyclic voltammetry(CV) and alternating current impedance(EIS) analysis show that Li_3VO_4 can increase Li+ conductivity, inhibit the side-effect between active material and electrolyte, and improve the electrochemical properties of materials.
The Li_3VO_4 coated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2 cathode material was synthesized by wet fusion technology and high temperature solid phase method. The crystalline phase, morphology and microstructure of materials were studied by X-ray diffraction(XRD), scanning electron microscope(SEM) and transmission electron microscope(TEM). The results show that Li_3VO_4 is evenly coated on the surface of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2 without changing the material structure and morphology of the raw materials. The coating thickness is 1—2 nm. The modification of Li Ni0.8 Co0.1 Mn0.1 O_2 cathode material with different content of Li_3VO_4 shows that 3%(mass) Li_3VO_4 coated Li Ni0.8 Co0.1 Mn0.1 O_2 has a capacity retention rate of 94.13% after 100 cycles under 1 C, which has the best multiplier performance and cycling performance. In addition, cyclic voltammetry(CV) and alternating current impedance(EIS) analysis show that Li_3VO_4 can increase Li+ conductivity, inhibit the side-effect between active material and electrolyte, and improve the electrochemical properties of materials.
引文
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[29]CHEN M,ZHAO E,CHEN D,et al.Decreasing Li/Ni disorder and improving the electrochemical performances of Ni-rich Li Ni0.8Co0.1Mn0.1O2 by Ca doping[J].Inorganic Chemistry,2017,56(14):8355-8362.
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[32]LI L,LI X,WANG Z,et al.A simple and effective method to synthesize layered LiNi0.8Co0.1Mn0.1O2 cathode materials for lithium ion battery[J].Powder Technology,2011,206(3):353-357.
[33]ZHANG C,LIU S,SU J,et al.Revealing the role of NH4VO3 treatment in Ni-rich cathode materials with improved electrochemical performance for rechargeable lithium-ion batteries[J].Nanoscale,2018,10:8820-8831.
[2]FERGUS J W.Recent developments in cathode materials for lithium ion batteries[J].Journal of Power Sources,2010,195(4):939-954.
[3]CHEN J.Recent progress in advanced materials for lithium ion batteries[J].Materials,2013,6(1):156-183.
[4]VU D L,LEE J W.Properties of LiNi0.8Co0.1Mn0.1O2 as a high energy cathode material for lithium-ion batteries[J].Korean Journal of Chemical Engineering,2016,33(2):514-526.
[5]DING Y,MU D,WU B,et al.Recent progresses on nickel-rich layered oxide positive electrode materials used in lithium-ion batteries for electric vehicles[J].Applied Energy,2017,195:586-599.
[6]WANG M,ZHANG R,GONG Y,et al.Improved electrochemical performance of the LiNi0.8Co0.1Mn0.1O2 material with lithium-ion conductor coating for lithium-ion batteries[J].Solid State Ionics,2017,312:53-60.
[7]LI X Q,XIONG X H,WANG Z X,et al.Effect of sintering temperature on cycling performance and rate performance of LiNi0.8Co0.1Mn0.1O2[J].Transactions of Nonferrous Metals Society of China,2014,24(12):4023-4029.
[8]LI C,ZHANG H P,FU L J,et al.Cathode materials modified by surface coating for lithium ion batteries[J].Electrochimica Acta,2006,51(19):3872-3883.
[9]XIONG X,WANG Z,YUE P,et al.Washing effects on electrochemical performance and storage characteristics of LiNi0.8Co0.1Mn0.1O2 as cathode material for lithium-ion batteries[J].Journal of Power Sources,2013,222:318-325.
[10]YUAN W,ZHANG H Z,LIU Q,et al.Surface modification of Li(Li0.17Ni0.2Co0.05Mn0.58)O2 with CeO2 as cathode material for Li-ion batteries[J].Electrochimica Acta,2014,135:199-207.
[11]LUO W,ZHENG B,HE J.Enhanced electrochemical performance of Li Ni0.5Co0.2Mn0.3O2,cathode material after surface modification with graphene oxide[J].Journal of Alloys and Compounds,2017,705:405-412.
[12]WANG Q,ZHANG C,XING J,et al.Direct synthesis of Al2O3-modified Li(Ni0.5Co0.2Mn0.3)O2,cathode materials for lithium ion batteries[J].Journal of Wuhan University of Technology(Materials Science Edition),2018,33(1):97-101.
[13]LI L,CHEN Z,ZHANG Q,et al.A hydrolysis-hydrothermal route for the synthesis of ultrathin LiAlO2-inlaid LiNi0.5Co0.2Mn0.3O2 as a highperformance cathode material for lithium ion batteries[J].Journal of Materials Chemistry A,2015,3(2):894-904.
[14]宋刘斌,刘姣,肖忠良,等.Li2ZrO3包覆Li Ni0.8Co0.1Mn0.1O2的复合材料及其电化学性能[J].化工学报,2017,68(11):4390-4397.SONG L B,LIU J,XIAO Z L,et al.Composite materials of Li2ZrO3coated LiNi0.8Co0.1Mn0.1O2 and its electrochemical properties[J].CIESC Journal,2017,68(11):4390-4397.
[15]YUAN S,LIU L B,TANG Y P,et al.Synthesis and electrochemical properties of cathode material LiNi0.8Co0.1Mn0.1O2 via Li,Mg,Al dopping[J].Advanced Materials Research,2014,1058:302-306.
[16]LI M,ZHOU Y,WU X,et al.The combined effect of CaF2 coating and La-doping on electrochemical performance of layered lithium-rich cathode material[J].Electrochimica Acta,2018,275:18-24.
[17]CHEN H,HU Q,HUANG Z,et al.Synthesis and electrochemical study of Zr-doped Li[Li0.2Mn0.54Ni0.13Co0.13]O2 as cathode material for Li-ion battery[J].Ceramics International,2016,42(1):263-269.
[18]LI Q,DANG R,CHEN M,et al.A synthesis method for long cycle life lithium-ion cathode material:Ni-rich core-shell LiNi0.8Co0.1Mn0.1O2[J].ACS Applied Materials&Interfaces,2018,10(21):17850-17860.
[19]LIAO J Y,OH S M,MANTHIRAM A.Core/double-shell type gradient Ni-rich LiNi0.76Co0.10Mn0.14O2 with high capacity and long cycle life for lithium-ion batteries[J].ACS Applied Materials&Interfaces,2016,8(37):24543-24549.
[20]KOMABA S,YABUUCHI N,NAKAYAMA T,et al.Study on the reversible electrode reaction of Na1-xNi0.5Mn0.5O2 for a rechargeable sodium-ion battery[J].Inorg.Chem.,2012,51(11):6211-6220.
[21]吴凯卓,王美,尚晓锋,等.锂离子电池低温电解液优化途径[J].电池工业,2017,21(4):50-53.WU Z K,WANG M,SHANG X F,et al.Optimization approach of low temperature electrolyte for lithium-ion batteries[J].Chinese Battery Industry,2017,21(4):50-53.
[22]宋秀芹,贾密英,陈汝芬.Li3VO4离子导体材料的合成及其离子导电性[J].中国有色金属学报,2000,10(4):591-595.SONG X Q,JIA M Y,CHEN R F.Synthesis and ionic conductivity of Li3VO4[J].The Chinese Journal of Nonferrous Metals,2000,10(4):591-595.
[23]LIAO C,WEN Y,XIA Z,et al.Si-doping mediated phase control fromβ-toγ-form Li3VO4 toward smoothing Li insertion/extraction[J].Advanced Energy Materials,2017:1701621-1701629.
[24]ZHANG B,DONG P,TONG H,et al.Enhanced electrochemical performance of Li Ni0.8Co0.1Mn0.1O2,with lithium-reactive Li3VO4coating[J].Journal of Alloys&Compounds,2017,706:198-204.
[25]HUANG Y,JIN F M,CHEN F J,et al.Improved cycle stability and high-rate capability of Li3VO4-coated Li[Ni0.5Co0.2Mn0.3]O2 cathode material under different voltages[J].Journal of Power Sources,2014,256:1-7.
[26]LIU X,SU Q,ZHANG C,et al.Enhanced electrochemical performance of Li1.2Mn0.54Ni0.13Co0.13O2 cathode with an ionic conductive LiVO3 coating layer[J].ACS Sustainable Chemistry&Engineering,2016,4(1):255-263.
[27]WANG W,YIN Z,WANG Z,et al.Effect of heat-treatment on electrochemical performance of Li3VO4-coated LiNi1/3Co1/3Mn1/3O2cathode materials[J].Materials Letters,2015,160:298-301.
[28]YANG P,LI H,WEI X,et al.Structure tuned Li1.2Mn0.6Ni0.2O2 with low cation mixing and Ni segregation as high performance cathode materials for Li-ion batteries[J].Electrochimica Acta,2018,271:276-283.
[29]CHEN M,ZHAO E,CHEN D,et al.Decreasing Li/Ni disorder and improving the electrochemical performances of Ni-rich Li Ni0.8Co0.1Mn0.1O2 by Ca doping[J].Inorganic Chemistry,2017,56(14):8355-8362.
[30]MENG K,WANG Z,GUO H,et al.Improving the cycling performance of LiNi0.8Co0.1Mn0.1O2 by surface coating with Li2TiO3[J].Electrochimica Acta,2016,211:822-831.
[31]XIAO Z,HU C,SONG L,et al.Modification research of LiAlO2-coated LiNi0.8Co0.1Mn0.1O2 as a cathode material for lithium-ion battery[J].Ionics,2017,24(1):91-98.
[32]LI L,LI X,WANG Z,et al.A simple and effective method to synthesize layered LiNi0.8Co0.1Mn0.1O2 cathode materials for lithium ion battery[J].Powder Technology,2011,206(3):353-357.
[33]ZHANG C,LIU S,SU J,et al.Revealing the role of NH4VO3 treatment in Ni-rich cathode materials with improved electrochemical performance for rechargeable lithium-ion batteries[J].Nanoscale,2018,10:8820-8831.