LiODFB基电解液与高电压正极材料LiNi_(0.5)Mn_(1.5)O_4的相容性
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摘要
研究了草酸二氟硼酸锂(LiODFB)基电解液与锂离子电池高电压正极材料锰酸镍锂(LiNi0.5Mn1.5O4)的相容性,结果表明:在25℃和60℃,以LiODFB和六氟磷酸锂(LiPF6)为电解液的LiNi0.5Mn1.5O4/Li电池的CV曲线都具有单一的氧化还原峰,电池的可逆性优良,且LiODFB电池的循环性能优于LiPF6电池。在25℃,LiODFB电池和LiPF6电池以0.5C倍率首次充放电比容量分别为126.3 mAh·g-1、131.6 mAh·g-1,经100次循环后容量保持率分别为97.1%、94.7%;在60℃,LiODFB电池和LiPF6电池以0.5C倍率首次充放电比容量分别为132.6 mAh·g-1、129.1 mAh·g-1,经100次循环后容量保持率分别为94.1%、81.7%。电化学阻抗谱也表明:在60℃,LiODFB电池的阻抗比LiPF6电池的小,LiODFB电池具有更好的高温充放电性能。
The compatibility of lithium difluoro(oxalato)borate(LiODFB) electrolyte with LiNi0.5Mn1.5O4 as high-voltage cathode material was investigated by cyclic voltammetry, charge-discharge test and AC impedance. The results show that the LiNi0.5Mn1.5O4/Li half cells with LiODFB or LiPF6 as electrolyte all have simple REDOX peak at 25℃ and 60℃, and the battery has an excellent reversibility. The battery with LiODFB has better cycle performance than that with LiPF6 at 25℃ and 60℃. Their 0.5C initial discharge specific capacities at 25℃ are 126.3 mAh?g-1and 131.6 mAh?g-1, and the capacity retention ratios by the 100 th cycle are 97.1 % and 94.7% respectively. The 0.5 C initial discharge specific capacities at60℃are 132.6 mAh·g-1and 129.1 mAh·g-1, and capacity retention ratios by the 100 th cycle are 94.1%and 81.7% respectively. AC impedance plots also show that the battery with LiODFB has a lower chargetransfer resistance than that with LiPF6 at 60℃, indicating that the battery with LiODFB has excellent cyclic performance at high temperature.
The compatibility of lithium difluoro(oxalato)borate(LiODFB) electrolyte with LiNi0.5Mn1.5O4 as high-voltage cathode material was investigated by cyclic voltammetry, charge-discharge test and AC impedance. The results show that the LiNi0.5Mn1.5O4/Li half cells with LiODFB or LiPF6 as electrolyte all have simple REDOX peak at 25℃ and 60℃, and the battery has an excellent reversibility. The battery with LiODFB has better cycle performance than that with LiPF6 at 25℃ and 60℃. Their 0.5C initial discharge specific capacities at 25℃ are 126.3 mAh?g-1and 131.6 mAh?g-1, and the capacity retention ratios by the 100 th cycle are 97.1 % and 94.7% respectively. The 0.5 C initial discharge specific capacities at60℃are 132.6 mAh·g-1and 129.1 mAh·g-1, and capacity retention ratios by the 100 th cycle are 94.1%and 81.7% respectively. AC impedance plots also show that the battery with LiODFB has a lower chargetransfer resistance than that with LiPF6 at 60℃, indicating that the battery with LiODFB has excellent cyclic performance at high temperature.
引文
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2 YI Tingfeng,YUE Caibo,HE Xiaojun,ZHU Rongsun,HU Xinguo,Review of research on synthesis and properties of LiNi0.5Mn1.5O4,Chinese Battery Industry,13(4),262(2008)(伊廷锋,岳彩波,何孝军,诸荣孙,胡信国,LiNi0.5Mn1.5O4材料合成及性能的研究综述,电池工业,13(4),262(2008))
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4 TANG Zhiyuan,HU Ran,WANG Lei,Research progress on LiNi0.5Mn1.5O4compound as 5V anode materials for lithium ion batteries,Chemical Industry and Engineering Progress,25(1),31(2006))(唐致远,胡冉,王雷,5V锂离子电池正极材料LiNi0.5Mn1.5O4的研究进展,化工进展,25(1),31(2006))
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6 YANG Xulai,WANG Yang,CAO Hekun,XU Xiaoming,Progress in high-voltage electrolytes for lithium ion batteries,Chinese Journal of Power Sources,36(8),1235(2012)(杨续来,汪洋,曹贺坤,徐小明,锂离子电池高电压电解液研究进展,电源技术,36(8),1235(2012))
7 TANG Zhiyuan,YANG Guangming,WANG Qian,Research progress in modif ication of LiNi0.5Mn1.5O4compound as 5V anode materials for lithium ion batteries,Materials Review,21(6),35(2007)(唐志远,杨光明,王倩,5V锂离子电池正极材料LiNi0.5Mn1.5O4改性研究现状,材料导报,21(6),35(2007))
8 Sheng Shui Zhang,An unique lithium salt for the improved electrolyte of Li-ion battery,Electrochemistry Communications,8(9),1423(2006)
9 M.H.Fu,K.L.Huang,S.Q.Liu,J.S.Liu,Y.K.Li,Lithium difluoro(oxalato)borate/ethylene carbonate+propylene carbonate+ethyl(methyl)carbonate electrolyte for LiMn2O4cathode,Journal of Power Sources,195(11),862(2010)
10 Sheng Shui Zhang,Electrochemical study of the formation of a solid electrolyte interface on graphite in a LiBC2O4F2-based electrolyte,Journal of Power Sources,163(7),713(2007)
11 CUI Xiaoling,LI Shiyou,LUO Jianguo,Research progress in electrolyte lithium salt lithium oxalyldifluoroborate,Battery Bimonthly,39(4),233(2009)(崔小玲,李世友,骆建国,电解质锂盐草酸二氟硼酸锂的研究进展,电池,39(4),233(2009))
12 Sheng Shui Zhang,K.Xu,T.R.Jow.Understanding Formation of Solid Electrolyte Interface Film on LiMn2O4Electrode,Journal of the Electrochemical Society,149(12),1521(2002)
13 XIE Hui,TANG Zhiyuan,LI Zhongyan,LiODFB:An unique lithium salt for lithium ion battery,New Chemical Materials,35(6),39(2007)(谢辉,唐致远,李中延,可用于锂离子电池的新型锂盐:LiODFB,化工新型材料,35(6),39(2007))
14 DENG Lingfeng,CHEN Hong,Electrochemical properties and synthesis of LiBC2O4F2for lithium batteries,Chinese Journal of Power Sources,34(3),237(2010)(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,34(3),237(2010))
15 Jie Li,Keyu Xie,Yanqing Lai,Zhi’an Zhang,Fanqun Li,Xin Hao,Xujie Chen,Yexiang Liu,Lithium oxalyldifluoroborate/carbonate electrolytes for LiFePO4/artificial graphite lithium-ion cells,Journal of Power Source,195(16),5344(2010)
16 Zhou Hongming,Fang Zhenqi,Li Jian.LiPF6and lithium difluoro(oxalato)borate/ethylene carbonate+dimethyl carbonate+ethyl(methyl)carbonate electrolyte for Li4Ti5O12anode,Journal of Power Sources,230,148(2013)
17 FU Maohua,HUANG Kelong,LIU Suqin,LIU Jiansheng,LI Yongkun,Effect of lithium difluoro(oxalato)borate on the high-temperature performance of LiFePO4/Graphite batteries,Acta Physico-Chimica Sinica,25(10),1985(2009)(付茂华,黄可龙,刘素琴,刘建生,李永坤,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,25(10),1985(2009))
2 YI Tingfeng,YUE Caibo,HE Xiaojun,ZHU Rongsun,HU Xinguo,Review of research on synthesis and properties of LiNi0.5Mn1.5O4,Chinese Battery Industry,13(4),262(2008)(伊廷锋,岳彩波,何孝军,诸荣孙,胡信国,LiNi0.5Mn1.5O4材料合成及性能的研究综述,电池工业,13(4),262(2008))
3 JI Yong,WANG Zhixing,YIN Zhoulan,GUO Huajun,PENG Wenjie,LI Xinhai,Synthesis and properties of cathode material LiNi0.5Mn1.5O4,Chinese Journal of Inorganic Chemistry,23(4),597(2007)(季勇,王志兴,尹周澜,郭华军,彭文杰,李新海,正极材料LiNi0.5Mn1.5O4的合成及性能,无机化学学报,23(4),597(2007))
4 TANG Zhiyuan,HU Ran,WANG Lei,Research progress on LiNi0.5Mn1.5O4compound as 5V anode materials for lithium ion batteries,Chemical Industry and Engineering Progress,25(1),31(2006))(唐致远,胡冉,王雷,5V锂离子电池正极材料LiNi0.5Mn1.5O4的研究进展,化工进展,25(1),31(2006))
5 FANG Haisheng,WANG Zhixing,LI Xinhai,GUO Huajun,PENG Wenjie,Synthesis and property of LiNi0.5Mn1.5O4for high-voltage lithium ion batteries,Chinese Battery Industry,11(1),36(2006)(方海升,王志兴,李新海,郭华军,彭文杰,高电压锂离子电池LiNi0.5Mn1.5O4的合成及性能,电池工业,11(1),36(2006))
6 YANG Xulai,WANG Yang,CAO Hekun,XU Xiaoming,Progress in high-voltage electrolytes for lithium ion batteries,Chinese Journal of Power Sources,36(8),1235(2012)(杨续来,汪洋,曹贺坤,徐小明,锂离子电池高电压电解液研究进展,电源技术,36(8),1235(2012))
7 TANG Zhiyuan,YANG Guangming,WANG Qian,Research progress in modif ication of LiNi0.5Mn1.5O4compound as 5V anode materials for lithium ion batteries,Materials Review,21(6),35(2007)(唐志远,杨光明,王倩,5V锂离子电池正极材料LiNi0.5Mn1.5O4改性研究现状,材料导报,21(6),35(2007))
8 Sheng Shui Zhang,An unique lithium salt for the improved electrolyte of Li-ion battery,Electrochemistry Communications,8(9),1423(2006)
9 M.H.Fu,K.L.Huang,S.Q.Liu,J.S.Liu,Y.K.Li,Lithium difluoro(oxalato)borate/ethylene carbonate+propylene carbonate+ethyl(methyl)carbonate electrolyte for LiMn2O4cathode,Journal of Power Sources,195(11),862(2010)
10 Sheng Shui Zhang,Electrochemical study of the formation of a solid electrolyte interface on graphite in a LiBC2O4F2-based electrolyte,Journal of Power Sources,163(7),713(2007)
11 CUI Xiaoling,LI Shiyou,LUO Jianguo,Research progress in electrolyte lithium salt lithium oxalyldifluoroborate,Battery Bimonthly,39(4),233(2009)(崔小玲,李世友,骆建国,电解质锂盐草酸二氟硼酸锂的研究进展,电池,39(4),233(2009))
12 Sheng Shui Zhang,K.Xu,T.R.Jow.Understanding Formation of Solid Electrolyte Interface Film on LiMn2O4Electrode,Journal of the Electrochemical Society,149(12),1521(2002)
13 XIE Hui,TANG Zhiyuan,LI Zhongyan,LiODFB:An unique lithium salt for lithium ion battery,New Chemical Materials,35(6),39(2007)(谢辉,唐致远,李中延,可用于锂离子电池的新型锂盐:LiODFB,化工新型材料,35(6),39(2007))
14 DENG Lingfeng,CHEN Hong,Electrochemical properties and synthesis of LiBC2O4F2for lithium batteries,Chinese Journal of Power Sources,34(3),237(2010)(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,34(3),237(2010))
15 Jie Li,Keyu Xie,Yanqing Lai,Zhi’an Zhang,Fanqun Li,Xin Hao,Xujie Chen,Yexiang Liu,Lithium oxalyldifluoroborate/carbonate electrolytes for LiFePO4/artificial graphite lithium-ion cells,Journal of Power Source,195(16),5344(2010)
16 Zhou Hongming,Fang Zhenqi,Li Jian.LiPF6and lithium difluoro(oxalato)borate/ethylene carbonate+dimethyl carbonate+ethyl(methyl)carbonate electrolyte for Li4Ti5O12anode,Journal of Power Sources,230,148(2013)
17 FU Maohua,HUANG Kelong,LIU Suqin,LIU Jiansheng,LI Yongkun,Effect of lithium difluoro(oxalato)borate on the high-temperature performance of LiFePO4/Graphite batteries,Acta Physico-Chimica Sinica,25(10),1985(2009)(付茂华,黄可龙,刘素琴,刘建生,李永坤,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,25(10),1985(2009))