固体电解质Li_5La_3Ta_2O_(12)包覆LiMn_2O_4的改性研究
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摘要
采用溶胶-凝胶的方法低温制备石榴石结构的固体电解质Li5La3Ta2O12,并用其包覆Li Mn2O4来改善材料的电化学性能。通过XRD,SEM和TEM等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安、交流阻抗等测试分析材料的电化学性能。研究结果表明:Li5La3Ta2O12包覆的Li Mn2O4材料与未包覆的材料相比,其电化学性能得到明显改善,经过150次循环后包覆材料的放电比容量保持率为92%,在高倍率10C(C为倍率)下包覆材料放电比容量为61.2 m A·h/g,而未包覆材料放电比容量仅为40.7 m A·h/g;包覆Li5La3Ta2O12后,Li Mn2O4的阻抗明显减小,大幅度提高了其循环性能和倍率性能。
Li Mn2O4,Li5La3Ta2O12(LLTO) was prepared by sol-gel method and it was employed as a coating layer on the surface of Li Mn2O4. The structure and morphology of the material were analyzed by XRD, SEM and other characterization methods. The electrochemical performance of the material was analyzed by galvanostatic charge-discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the electrochemical performance of the LLTO-coated Li Mn2O4 is improved significantly. The resistance of LLTO-coated Li Mn2O4 is reduced significantly. After 150 cycles test, the discharge capacity retention rate of the coated material is92%.At the high-rate of 10 C, the discharge capacity of the LLTO-coated Li Mn2O4 is 61.2 m A·h/g and that of the uncoated material is 40.7 m A·h/g. The impedance of LLTO-coated Li Mn2O4 decreases evidently, therefore the cycle performance and rate capability increase greatly.
Li Mn2O4,Li5La3Ta2O12(LLTO) was prepared by sol-gel method and it was employed as a coating layer on the surface of Li Mn2O4. The structure and morphology of the material were analyzed by XRD, SEM and other characterization methods. The electrochemical performance of the material was analyzed by galvanostatic charge-discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the electrochemical performance of the LLTO-coated Li Mn2O4 is improved significantly. The resistance of LLTO-coated Li Mn2O4 is reduced significantly. After 150 cycles test, the discharge capacity retention rate of the coated material is92%.At the high-rate of 10 C, the discharge capacity of the LLTO-coated Li Mn2O4 is 61.2 m A·h/g and that of the uncoated material is 40.7 m A·h/g. The impedance of LLTO-coated Li Mn2O4 decreases evidently, therefore the cycle performance and rate capability increase greatly.
引文
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[25]Aurbach D,Levi M D,Gamulski K,et al.Capacity fading of Lix Mn2O4 spinel electrodes studied by XRD and electroanalytical techniques[J].Journal of Power Sources,1999,81(8):472-479.
[26]Aurbach D,Levi M D,Levi E,et al.Common electroanalytical behavior of Li intercalation processes into graphite and transition metal oxides[J].Journal of the Electrochemical Society,1998,145(9):3024-3034.
[2]Thackeray M M.Manganese oxides for lithium batteries[J].Progress in Solid State Chemistry,1997,25(1):1-71.
[3]陈立宝,贺跃辉,汤义武.采用固相配位法制备超细Li Mn2O4正极材料[J].中南大学学报(自然科学版),2005,36(3):390-395.CHEN Libao,HE Yuehui,TANG Yiwu.Preparation of ultrafine Li Mn2O4 cathode materials by solid state coordination method[J].Journal of Central South University(Science and Technology),2005,36(3):390-395.
[4]Thackeray M M.Structural considerations of layered and spinel lithiated oxides for lithium ion batteries[J].Journal of the Electrochemical Society,1995,142(8):2558-2563.
[5]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.
[6]SUN Huaibing,CHEN Yungui,XU Chenghao,et al.Electrochemical performance of rare-earth doped Li Mn2O4spinel cathode materials for Li-ion rechargeable battery[J].Journal of Solid State Electrochemistry,2012,16(3):1247-1254.
[7]Hibino M,Nakamura M,Kamitaka Y,et al.Improvement of cycle life of spinel type of lithium manganese oxide by addition of other spinel compounds during synthesis[J].Solid State Ionics,2006,177(26/32):2653-2656.
[8]LIU Dongqiang,LIU Xingquan,HE Zezheng.Surface modification by Zn O coating for improving the elevated temperature performance of Li Mn2O4[J].Journal of Alloys and Compounds,2007,436(1):387-391.
[9]LIU Dongqiang,HE Zeqiang.Increased cycling stability of Al PO4-coated Li Mn2O4 for lithium ion batteries[J].Materials Letters,2007,61(25):4703-4706.
[10]Moon H S,Lee S W,Lee Y K,et al.Characterization of protective-layer-coated Li Mn2O4 cathode thin films[J].Journal of Power Sources,2003,119(10/11):713-716.
[11]LIU Jinlian,WU Xianming,CHEN Shang,et al.Enhanced high temperature performance of Li Mn2O4 coated with Li3BO3 solid electrolyte[J].Bulletin of Materials Science,2013,36(4):687-691.
[12]Kim W K,Han D W,Ryu W H,et al.Al2O3 coating on Li Mn2O4by electrostatic attraction forces and its effects on the high temperature cyclic performance[J].Electrochimica Acta,2012,71:17-21.
[13]Arumugam D,Kalaignan G P.Synthesis and electrochemical characterization of nano-Ce O2-coated nanostructure Li Mn2O4cathode materials for rechargeable lithium batteries[J].Electrochimica Acta,2010,55(28):8709-8716.
[14]MING Hai,YAN Yuerong,MING Jun,et al.Gradient V2O5surface-coated Li Mn2O4 cathode towards enhanced performance in Li-ion battery applications[J].Electrochimica Acta,2014,120:390-397.
[15]Ha H W,YUN Nanji,Kim K.Improvement of electrochemical stability of Li Mn2O4 by Ce O2 coating for lithium-ion batteries[J].Electrochimica Acta,2007,52(9):3236-3241.
[16]LIU Qiuling,WANG Shengping,TAN Haibo,et al.Preparation and doping mode of doped Li Mn2O4 for Li-Ion batteries[J].Energies,2013,6(3):1718-1730.
[17]吴显明,谭磊,李明,等.固体电解质包覆Li Mn2O4正极材料的合成及表征[J].精细化工,2011,28(2):116-119.WU Xianming,TAN Lei,LI Ming,et al.Synthesis and characterization of the cathode material of Li Mn2O4 coated by solid electrolyte[J].Fine Chemicals,2011,28(2):116-119.
[18]PENG Hongjian,WU Qing,XIAO Lihong.Low temperature synthesis of Li5La3Nb2O12 with cubic garnet-type structure by sol–gel process[J].Journal of Sol–Gel Science and Technology,2013,66(1):175-179.
[19]O’Callaghan M P,Lynham D R,Cussen E J,et al.Structure and ionic-transport properties of lithium-containing garnet Li3Ln3Te2O12(Ln=Y,Pr,Nd,Sm-Lu)[J].Chemistry of Materials,2006,18(19):4681-4689.
[20]Thangadurai V,Kaack H,Weppner W.Novel fast lithium ion conduction in garnet-type Li5La3M2O12(M=Nb,Ta)[J].Journal of the American Ceramic Society,2003,86(3):437-440.
[21]Gnanaraj J S,Pol V G,Gedanken A,et al.Improving the high-temperature performance of Li Mn2O4 spinel electrodes by coating the active mass with Mg O via a sonochemical method[J].Electrochemistry Communications,2003,5(11):940-945.
[22]Eriksson T,Hjelm A K,Lindbergh G,et al.Kinetic study of Li Mn2O4 cathodes by In situ XRD with constant-current cycling and potential stepping[J].Journal of the Electrochemical Society,2002,149(9):A1164-A1170.
[23]Liu W,Farrington G C,Chaput F,et al.Synthesis and electrochemical studies of spinel phase Li Mn2O4 cathode materials prepared by the pechini process[J].Journal of the Electrochemical Society,1996,143(3):879-884.
[24]Aurbach D,Gamolsky K,Markovsky B,et al.The study of surface phenomena related to electrochemical lithium intercalation into Lix MOy host materials(M=Ni,Mn)[J].Journal of the Electrochemical Society,2000,147(4):1322-1331.
[25]Aurbach D,Levi M D,Gamulski K,et al.Capacity fading of Lix Mn2O4 spinel electrodes studied by XRD and electroanalytical techniques[J].Journal of Power Sources,1999,81(8):472-479.
[26]Aurbach D,Levi M D,Levi E,et al.Common electroanalytical behavior of Li intercalation processes into graphite and transition metal oxides[J].Journal of the Electrochemical Society,1998,145(9):3024-3034.