LiODFB基电解液的电化学性能及其与钛酸锂的相容性研究
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摘要
采用电化学工作站测试了1 mol/L LiODFB(LiPF6)EC+DMC+EMC(1:1:1质量比)电解液的热稳定性及其对铝箔集流体的腐蚀性,测试了LTO/Li电池的CV曲线及EIS图谱,并采用电池性能测试系统测试电池的倍率性能和循环性能,探索LiODFB电解液与LiFePO4/LTO电极的相容性。结果表明:在室温和60℃条件下,LiODFB电解液及其对铝箔的稳定性均优于LiPF6电解液,以LiODFB和LiPF6为电解液的LTO/Li电池的CV曲线都具有单一的氧化还原峰,且其首次充放曲线均具有稳定的充放电平台,室温时以LiFePO4/LTO为电极的LiODFB电池和LiPF6电池在0.5C和1C倍率的电池性能相差不大;室温和60℃时LiODFB电池的循环性能均优于LiPF6电池,60℃时尤为显著。
1 mol/L LiODFB(LiPF6) EC+DMC+EMC(1:1:1(wt%)) electrolyte’s thermal stability and corrosivity to the aluminum foil were tested by the electrochemical workstation.Cyclic voltammogram,electrochemical impedance spectroscopy rate and cycle performances of LTO/Li battery were measured.The compatibility between LiFePO4/LTO electrode and electrolyte was studied.Results show that at room temperature and 60℃,the stability of LiODFB electrolyte and its corrosivity to the aluminum foil are superior to that of LiPF6 electrolyte.LTO/Li cells with either LiODFB or LiPF6 for electrolyte have simple REDOX peak,and their first charge-discharge curves have stable charge-discharge platform.The difference battery performance between LiODFB and LiPF6 with LiFePO4/LTO as electrode at 0.5C and 1C rates is not significant at room temperature.LiODFB battery exhibits better cycle performance than LiPF6battery at room temperature and especially at 60℃.
1 mol/L LiODFB(LiPF6) EC+DMC+EMC(1:1:1(wt%)) electrolyte’s thermal stability and corrosivity to the aluminum foil were tested by the electrochemical workstation.Cyclic voltammogram,electrochemical impedance spectroscopy rate and cycle performances of LTO/Li battery were measured.The compatibility between LiFePO4/LTO electrode and electrolyte was studied.Results show that at room temperature and 60℃,the stability of LiODFB electrolyte and its corrosivity to the aluminum foil are superior to that of LiPF6 electrolyte.LTO/Li cells with either LiODFB or LiPF6 for electrolyte have simple REDOX peak,and their first charge-discharge curves have stable charge-discharge platform.The difference battery performance between LiODFB and LiPF6 with LiFePO4/LTO as electrode at 0.5C and 1C rates is not significant at room temperature.LiODFB battery exhibits better cycle performance than LiPF6battery at room temperature and especially at 60℃.
引文
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[20]郑洪河.锂离子电池电解质.北京:化学工业出版社,2007:26–29.
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[2]GAO Hong-quan,ZHANG Zhi-an,LAI Yan-qing.Structure char-acterization and electrochemical properties of new lithium saltLiODFB for electrolyte of lithium ion batteries.J.Cent.SouthUniv.Technol.,2008,15(23):830–834.
[3]邓凌峰,陈洪.锂离子电池电解质LiBC2O4F2的合成与电化学性能.电源技术,2010,34(3):237–240.
[4]Zhang S S.Electrochemical study of the formation of a solid elec-trolyte interface on graphite in a LiBC2O4F2-based electrolyte.Journal of Power Sources,2007,163(7):713–718.
[5]付茂华.磷酸铁锂电池用高低温电解液的研究.长沙:中南大学硕士论文,2010.
[6]FU M H,HUANG K L,LIU S Q,et al.Lithium difluoro(oxalato)borate/ethylene carbonate+propylene carbonate+ethyl(methyl)carbonate electrolyte for LiMn2O4 cathode.Journal of PowerSources,2010,195(11):862–866.
[7]Zhang S S,Xu K,Jow T R.Understanding formation of solid elec-trolyte interface film on LiMn2O4 electrode.Journal of the Elec-trochemical Society,2002,149(12):1521–1526.
[8]Liu J,Chen Z H,Sara B,et al.Lithium difluoro(oxalato)borate as afunctional additive for lithium-ion batteries.ElectrochemistryCommunications,2007,9(3):475–479.
[9]Ohzuku T,Ueda A,Yamamoto N.Zero-strain insertion material ofLi[Li1/3Ti5/3]O4 for rechargeable lithium cells.J.Electrochem Soc.,1995,142(5):1431–1435.
[10]Kanamura K,Umegak T,Naito H,et al.Structural and electro-chemical characteristics of Li4/3Ti5/3O4 as an anode material forrechargeable lithium batteries.Journal of Applied Electrochemistry,2001,31(14):73–78.
[11]CHENG Liang,LIU Hai-jing,ZHANG Jing-jun.NanosizedLi4Ti5O12 prepared by molten salt method as an electrode materialfor hybrid electrochemical super capacitors.Journal of The Elec-trochemical Society,2006,153(8):A1472–A1477.
[12]HUANG S H,WEN Z Y,ZHU X J.Preparation and electrochemi-cal performance of Ag doped Li4Ti5O12.Electrochemistry Commu-nications,2004,6(11):1093–1097.
[13]Young Ho Rho,Kiyoshi Kanamura,Minori Fujisaki,et al.Prepa-ration of Li4Ti5O12 and LiCoO2 thin film electrodes from precur-sors obtained by Sol-Gel method.Solid State Ionics,2002,151(22):151–157.
[14]Jiang C H,Ichihara M,Honma I,et al.Effect of particle dispersionon high rate performance of nano-sized Li4Ti5O12 anode.Electro-chimica Acta,2007,52(12):6470–6475.
[15]Nakahara K,Nakajima R,Matsushima T,et al.Preparation of par-ticulate Li4Ti5O12 having excellent characteristics as an electrodeactive material for power storage cells.J.Power Sources,2003,117(23):131–136.
[16]李凡群.LiODFB基电解液及其与LiFePO4-AC/AG-AC超级电容电池电极材料的相容性研究.长沙:中南大学硕士论文,2009.
[17]付茂华,黄可龙,刘素琴,等(Fu Mao-Hua,et al).二氟二草酸硼酸锂对LiFePO4/石墨电池高温性能的影响.物理化学学报(Acta Phys.Chim.Sinica),2009,25(10):1985–1990.
[18]LI J,XIE K X,LAI Y Q,et al.Lithium oxalyldifluoroborate/car-bonate electrolytes for LiFePO4/artificial graphite lithium-ion cells.Journal of Power Source,2010,195(16):5344–5350.
[19]陈凤凤.锂离子电池中新型电解质的合成与表征.南京:南京师范大学硕士论文,2010.
[20]郑洪河.锂离子电池电解质.北京:化学工业出版社,2007:26–29.
[21]HUI Yang,GUO Rong,Philip N,et al.Thermal stability of LiPF6salt and Li-ion battery electrolytes containing LiPF6.Journal ofPower Sources,2006,161(15):573–579.
[22]Ohzuku T,Ueda A,Yamamot N,et al.Factor affecting the capacity re-tention of lithium-ion cells.Solid State Ionics,1994,69(24):201–211.