LiPF_6 and lithium difluoro(oxalato)borate/ethylene carbonate+dimethyl carbonate +ethyl(methyl)carbonate electrolyte for LiNi_(0.5)Mn_(1.5)O_4 cathode
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摘要
LiODFB electrolyte's compatibility with LiNi_(0.5)Mn_(1.5)O_4 high-voltage cathode material was studied by cyclic voltammetry, charge-discharge test and AC impedance. The results show that at 25 and 60 °C, the LiODFB-based electrolyte has better electrochemical stability than LiPF_6. AC impedance plots show that the LiODFB battery has a lower charge-transfer resistance than LiPF_6 battery at 60 °C, which indicates that LiODFB battery has excellent cycling performance at high temperature. At 25 and 60 °C, the LiNi_(0.5)Mn_(1.5)O_4/Li half cells with Li ODFB or LiPF_6 as electrolyte all have simple redox peak, showing that each of them has an excellent reversibility. LiODFB battery has better cycle performance than LiPF_6 battery at 25 °C and 60 °C. At 25 °C, their 0.5C initial discharge specific capacities are 126.3 and 131.6 m A·h/g, and their capacity retention ratios of the 100 th cycle are 97.1% and 94.7%, respectively. At 60 °C, their 0.5C initial discharge specific capacities are 132.6 and 129.1 m A·h/g, and their capacity retention ratios of the 100 th cycle are 94.1% and 81.7%, respectively.
LiODFB electrolyte's compatibility with LiNi_(0.5)Mn_(1.5)O_4 high-voltage cathode material was studied by cyclic voltammetry, charge-discharge test and AC impedance. The results show that at 25 and 60 °C, the LiODFB-based electrolyte has better electrochemical stability than LiPF_6. AC impedance plots show that the LiODFB battery has a lower charge-transfer resistance than LiPF_6 battery at 60 °C, which indicates that LiODFB battery has excellent cycling performance at high temperature. At 25 and 60 °C, the LiNi_(0.5)Mn_(1.5)O_4/Li half cells with Li ODFB or LiPF_6 as electrolyte all have simple redox peak, showing that each of them has an excellent reversibility. LiODFB battery has better cycle performance than LiPF_6 battery at 25 °C and 60 °C. At 25 °C, their 0.5C initial discharge specific capacities are 126.3 and 131.6 m A·h/g, and their capacity retention ratios of the 100 th cycle are 97.1% and 94.7%, respectively. At 60 °C, their 0.5C initial discharge specific capacities are 132.6 and 129.1 m A·h/g, and their capacity retention ratios of the 100 th cycle are 94.1% and 81.7%, respectively.
LiODFB electrolyte's compatibility with LiNi_(0.5)Mn_(1.5)O_4 high-voltage cathode material was studied by cyclic voltammetry, charge-discharge test and AC impedance. The results show that at 25 and 60 °C, the LiODFB-based electrolyte has better electrochemical stability than LiPF_6. AC impedance plots show that the LiODFB battery has a lower charge-transfer resistance than LiPF_6 battery at 60 °C, which indicates that LiODFB battery has excellent cycling performance at high temperature. At 25 and 60 °C, the LiNi_(0.5)Mn_(1.5)O_4/Li half cells with Li ODFB or LiPF_6 as electrolyte all have simple redox peak, showing that each of them has an excellent reversibility. LiODFB battery has better cycle performance than LiPF_6 battery at 25 °C and 60 °C. At 25 °C, their 0.5C initial discharge specific capacities are 126.3 and 131.6 m A·h/g, and their capacity retention ratios of the 100 th cycle are 97.1% and 94.7%, respectively. At 60 °C, their 0.5C initial discharge specific capacities are 132.6 and 129.1 m A·h/g, and their capacity retention ratios of the 100 th cycle are 94.1% and 81.7%, respectively.
引文
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[8]YANG Xu-lai,WANG Yang,CAO He-kun,XU Xiao-ming.Progress in high-voltage electrolytes for lithium ion batteries[J].Chinese Journal of Power Sources,2012,36(8):1235-1238.(in Chinese)
[9]ZHANG Sheng-shui.An unique lithium salt for the improved electrolyte of Li-ion battery[J].Electrochemistry Communications,2006,8(9):1423-1428.
[10]ZHANG S S,XU K,JOW T R.A new approach toward improved low temperature performance of Li-ion battery[J].Electrochemistry Communications,2002,4(11):928-932.
[11]XU K,ZHANG S S,LEE U,ALLEN J L,JOW T R.Li BOB:Is it an alternative salt for lithium ion chemistry[J].Journal of Power Sources,2005,146(1):79-85.
[12]FU M H,HUANG K L,LIU S Q,LIU L S,LI Y K.Lithium difluoro(oxalato)borate/ethylene carbonate+propylene carbonate+ethyl(methyl)carbonate electrolyte for Li Mn2O4 cathode[J].Journal of Power Sources,2010,195(3):862-866.
[13]ZHANG Zhi-an,CHEN Xu-jie,LI Fan-qun,LAI Yan-qing,LI Jie,LIU Ping,WANG Xin-yu.Li PF6 and lithium oxalyldifluoroborate blend salts electrolyte for Li Fe PO4/artificial graphite lithium-ion cells[J].Journal of Power Sources,2010,195(21):7397-7402.
[14]GAO Hong-quan,ZHANG Zhi-an,LAI Yan-qing,LI Jie,LIU Ye-xiang.Structure characterization and electrochemical properties of new lithium salt Li ODFB for electrolyte of lithium ion batteries[J].Journal of Central South University of Technology,2008,15:830-834.
[15]ZHOU Hong-ming,FANG Zhen-qi,LI Jian.Li PF6 and lithium difluoro(oxalato)borate/ethylene carbonate+dimethyl carbonate+ethyl(methyl)carbonate electrolyte for Li4Ti5O12 anode[J].Journal of Power Sources,2013,230:148-154.
[2]MIERLO J V,den BOSSCHE P V,MAGGETTO G.Models of energy sources for EV and HEV:Fuel cells,batteries,ultracapacitors,flywheels and engine-generators[J].Journal of Power Sources,2004,128(1):76-89.
[3]ARAI J,YAMAKI T,YAMAUCHI S,YUASA T,MAESHIMA T,SAKAI T,KOSEKI M,HORIBA T.Development of a high power lithium secondary battery for hybrid electric vehicles[J].Journal of Power Sources,2005,146(1):788-792.
[4]BENINATI S,DAMEN L,MASTRAGOSTINO M.Fast sol-gel synthesis of Li Fe PO4/C for high power lithium-ion batteries for hybrid electric vehicle application[J].Journal of Power Sources,2009,194(2):1094-1098.
[5]SANTHANAM R,RAMBABU B.Research progress in high voltage spinel Li Ni0.5Mn1.5O4 material[J].Journal of Power Sources,2010,195(17):5442-5451.
[6]KIM M C,KIM S H,ARAVINDAN V,KIM W S,LEE S Y.Ultrathin polyimide coating for a spinel lini0.5mn1.5o4 cathode and its superior lithium storage properties under elevated temperature conditions[J].Journal of the Electrochemical Society,2013,160(8):1003-1008.
[7]AKLALOUCH M,AMARILLA J M,ROJAS R M,SAADOUNE I,ROJO J M.Chromium doping as a new approach to improve the cycling performance at high temperature of 5 V Li Ni0.5Mn1.5O4-based positive electrode[J].Journal of Power Sources,2008,185(1):501-511.
[8]YANG Xu-lai,WANG Yang,CAO He-kun,XU Xiao-ming.Progress in high-voltage electrolytes for lithium ion batteries[J].Chinese Journal of Power Sources,2012,36(8):1235-1238.(in Chinese)
[9]ZHANG Sheng-shui.An unique lithium salt for the improved electrolyte of Li-ion battery[J].Electrochemistry Communications,2006,8(9):1423-1428.
[10]ZHANG S S,XU K,JOW T R.A new approach toward improved low temperature performance of Li-ion battery[J].Electrochemistry Communications,2002,4(11):928-932.
[11]XU K,ZHANG S S,LEE U,ALLEN J L,JOW T R.Li BOB:Is it an alternative salt for lithium ion chemistry[J].Journal of Power Sources,2005,146(1):79-85.
[12]FU M H,HUANG K L,LIU S Q,LIU L S,LI Y K.Lithium difluoro(oxalato)borate/ethylene carbonate+propylene carbonate+ethyl(methyl)carbonate electrolyte for Li Mn2O4 cathode[J].Journal of Power Sources,2010,195(3):862-866.
[13]ZHANG Zhi-an,CHEN Xu-jie,LI Fan-qun,LAI Yan-qing,LI Jie,LIU Ping,WANG Xin-yu.Li PF6 and lithium oxalyldifluoroborate blend salts electrolyte for Li Fe PO4/artificial graphite lithium-ion cells[J].Journal of Power Sources,2010,195(21):7397-7402.
[14]GAO Hong-quan,ZHANG Zhi-an,LAI Yan-qing,LI Jie,LIU Ye-xiang.Structure characterization and electrochemical properties of new lithium salt Li ODFB for electrolyte of lithium ion batteries[J].Journal of Central South University of Technology,2008,15:830-834.
[15]ZHOU Hong-ming,FANG Zhen-qi,LI Jian.Li PF6 and lithium difluoro(oxalato)borate/ethylene carbonate+dimethyl carbonate+ethyl(methyl)carbonate electrolyte for Li4Ti5O12 anode[J].Journal of Power Sources,2013,230:148-154.