xLi_3V_2(PO_4)_3·LiVPO_4F/C复合正极材料的合成及储锂性能
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摘要
用乙炔碳作为碳源,采用机械活化辅助碳热还原两步法合成xLi_3V_2(PO_4)_3·LiVPO_4F/C复合正极材料。采用XRD、SEM、TEM等技术对样品的晶体结构和微观形貌进行了表征,采用循环伏安法和恒流充放电等测试方法对合成样品的电化学性能进行分析研究。结果表明:xLi_3V_2(PO_4)_3·LiVPO_4F/C复合正极材料兼备了Li_3V_2(PO_4)_3的循环稳定性好、倍率性能佳的优点和LiVPO_4F能量密度高的优势,此外还弥补了Li_3V_2(PO_4)_3在3～4.7 V电压范围充放电时放电电压平台缺失的缺陷。该材料在3～4.7 V之间的循环稳定性较好,在1C倍率下最高放电比容量为119.7 m A·h/g,循环300圈后为97.5 m A·h/g。其倍率性能较好,在0.1C倍率下充放电可获得高达152 m A·h/g的放电比容量,倍率升高到8C时仍能保持100 mA·h/g的放电比容量。
A two-step mechanical activation and carbon thermal reduction method was used to synthesize xLi_3V_2(PO_4)_3·LiVPO_4F/C composite cathode material, using actylene black as carbon source. The crystal structure and morphology were characterized by using XRD, SEM, and TEM techniques. In addition, the electrochemical performances of the prepared materials were characterized by cyclic voltammetry(CV) and galvanostatic charge/discharge tests. The results show that xLi_3V_2(PO_4)_3LiVPO_4F/C composite cathode material has the advantages of good cyclic stability of Li_3 V_2(PO_4)_3 and the high energy density of LiVPO_4F. Meanwhile, it makes up for the shortcoming of the disappeared voltage platform of Li_3 V_2(PO_4)_3 cathode within 3-4.7 V. The cyclic stability of the composite is good. The maximum value of discharge specific capacity is 119.7 mA·h/g under the rate of 1 C which can retain 97.5 mA·h/g after 300 cycles. The rate performance is excellent. The composite electrode delivers a high capacity of 152 m A·h/g at 0.1 C. When the current density increases to 8 C, the electrode can still deliver a specific discharge capacity of 100 mA·h/g.
A two-step mechanical activation and carbon thermal reduction method was used to synthesize xLi_3V_2(PO_4)_3·LiVPO_4F/C composite cathode material, using actylene black as carbon source. The crystal structure and morphology were characterized by using XRD, SEM, and TEM techniques. In addition, the electrochemical performances of the prepared materials were characterized by cyclic voltammetry(CV) and galvanostatic charge/discharge tests. The results show that xLi_3V_2(PO_4)_3LiVPO_4F/C composite cathode material has the advantages of good cyclic stability of Li_3 V_2(PO_4)_3 and the high energy density of LiVPO_4F. Meanwhile, it makes up for the shortcoming of the disappeared voltage platform of Li_3 V_2(PO_4)_3 cathode within 3-4.7 V. The cyclic stability of the composite is good. The maximum value of discharge specific capacity is 119.7 mA·h/g under the rate of 1 C which can retain 97.5 mA·h/g after 300 cycles. The rate performance is excellent. The composite electrode delivers a high capacity of 152 m A·h/g at 0.1 C. When the current density increases to 8 C, the electrode can still deliver a specific discharge capacity of 100 mA·h/g.
引文
[1]ZHANG Hui-gang,YU Xin-di,BRAUN P V.Three-dimensional continuous ultrafast charge and discharge bulk battery electrodes[J].Nature Nanotechnology,2011,6(5):277-281.
[2]ZAGHIB K,MAUGER A,GROULT H,GOODENOUGH J B,JULIEN C M.Advanced electrodes for high power Li-ion batteries[J].Materials,2013,6(3):1028-1049.
[3]CHERNOVA N A,ROPPOLO M,DILLON A C,WHITTINGHAM M S.Layered vanadium and molybdenum oxides:batteries and electrochromics[J].Journal of Materials Chemistry,2009,19(17):2526-2552.
[4]THAPA A K.Development of cathode materials for Li-ion battery and megalo-capacitance capacitor[D].Saga:Saga University,2007.
[5]XU Bo,QIAN Dan-na,WANG Zi-ying,MENG Y S.Recent progress in cathode materials research for advanced lithium ion batteries[J].Materials Science and Engineering,2012,73(5):51-65.
[6]HE Ping,YU Hai-jun,LI De,ZHOU Hao-shen.Layered lithium transition metal oxide cathodes towards high energy lithium-ion batteries[J].Journal of Materials Chemistry,2012,22(9):3680-3695.
[7]LIU W,OH P L,LIU X,LEE M J,CHO W G,CHAE S J,KIMY S,CHO J P.Nickel-rich layered lithium transition-metal oxide for high-energy lithium‐ion batteries[J].Angewandte Chemie International Edition,2015,54(15):4440-4457.
[8]CHEN Jia-jun.Recent progress in advanced materials for lithium ion batteries[J].Materials,2013,6(1):156-183.
[9]PAN A Q,CHOI D,ZHANG J G,LIANG S Q,CAO G Z,NIE ZM,AREY B W,LIU J.High-rate cathodes based on Li3V2(PO4)3nanobelts prepared via surfactant-assisted fabrication[J].Journal of Power Sources,2011,196(7):3646-3649.
[10]PAN An-qiang,LIU Jun,ZHANG Ji-gang,XU Wu,CAOGuo-zhong,NIE Zi-min,AREY B W,LIANG Shu-quan.Nano-structured Li3V2(PO4)3/carbon composite for high-rate lithium-ion batteries[J].Electrochemistry Communications,2010,12(12):1674-1677.
[11]YIN S C,STROBEL P S,GRONDEY H,NAZAR L F.Li2.5V2(PO4)3:A room-temperature analogue to the fast-ion conducting high-temperatureγ-phase of Li3V2(PO4)3[J].Chemistry of Materials,2004,16(8):1456-1465.
[12]BARKER J,SAIDI M Y,SWOYER J L.Electrochemical insertion properties of the novel lithium vanadium fluorophosphate,LiVPO4F[J].Journal of the Electrochemical Society,2003,150(10):A1394-A1398.
[13]GOVER R K B,BURNS P,BRYAN A,SAIDI S Y,SWOYER JL,BARKER J.LiVPO4F:A new active material for safe lithium-ion batteries[J].Solid State Ionics,2006,177(26):2635-2638.
[14]WANG Jie-xi,WANG Zhi-xing,Ll Xin-hai,GUO Hua-jun,XUXian-wen,ZHANG Xiao-ping,XIAO Wei.x Li3V2(PO4)3·LiVPO4F/C composite cathode materials for lithium ion batteries[J].Electrochimica Acta,2013,87:224-229.
[15]WANG Ren-heng,XIAO Shun-hua LI Xin-hai,WANG Jie-xi,GUO Hua-jun,ZHONG Fu-xin.Structural and electrochemical performance of Na-doped Li3V2(PO4)3/C cathode materials for lithium-ion batteries via rheological phase reaction[J].Journal of Alloys and Compounds,2013,575:268-272.
[16]LIU Zhao-meng,PENG Wen-jie,SHIH Kai-min,WANG Jie-xi,WANG Zhi-xing,GUO Hua-jun,YAN Guo-chun,LI Xin-hai,SONG Liu-bin.A MoS2 coating strategy to improve the comprehensive electrochemical performance of LiVPO4F[J].Journal of Power Sources,2016,315:294-301.
[17]LIM H H,CHO A R,SIVAKUMAR N,KIM W S,YOON W S,LEE Y S.Improved rate capability of Li/Li3V2(PO4)3 cell for advanced lithium secondary battery[J].Bulletin of Korean Chemical Society,2011,32:1491-1494.
[18]BARKER J,GOVER R K B,BURNS P,BRYAN A,SAIDI M Y,SWOYER J L.Structural and electrochemical properties of lithium vanadium fluorophosphate,LiVPO4F[J].Journal of Power Sources,2005,146:516-520.
[19]WU Ling,LU Jia-jia,ZHONG Sheng-kui.Studies of x Li Fe PO4·y Li3V2(PO4)3/C composite cathode materials with high tap density and high performance prepared by sol spray drying method[J].Journal of Solid State Electrochemistry,2013,17(8):2235-2241.
[20]QIN Lai-fen,XIA Yong-gao,QIU Bao,CAO Hai-liang,LIUYuan-zhuang,LIU Zhao-ping.Synthesis and electrochemical performances of(1-x)LiMnPO4·x Li3V2(PO4)3/C composite cathode materials for lithium ion batteries[J].Journal of Power Sources,2013,239:144-150.
[21]LIN Y C,FEY G T K,WU P J,CHANG J K,KAO H M.Synthesis and electrochemical properties of x Li Fe PO4·(1-x)LiVPO4F composites prepared by aqueous precipitation and carbothermal reduction[J].Journal of Power Sources,2013,244:63-71.
[22]ZHANG Bao,SHEN Chao,ZHENG Jun-chao,HAN Ya-dong,ZHANG Jia-feng,MING Lei,WANG Jian-long,QIN Sha-ne,LIHui.Synthesis and characterization of a multi-layer core-shell composite cathode material LiVOPO4-Li3V2(PO4)3[J].Journal of The Electrochemical Society,2014,161(5):A748-A752.
[23]HUANG Huan,YIN S C,KERR T,TAYLOR N,NAZAR L F.Nanostructured composites:A high capacity,fast rate Li3V2(PO4)3/carbon cathode for rechargeable lithium batteries[J].Advanced Materials,2002,14(21):1525-1528.
[24]FEY G T K,LU T L,WU F Y,LI W H.Carboxylic acid-assisted solid-state synthesis of LiFePO4/C composites and their electrochemical properties as cathode materials for lithium-ion batteries[J].Journal of Solid State Electrochemistry,2008,12(7/8):825-833.
[25]ATEBA MBA J M,MASQUELIER C,SUARD E,CROGUENNEC L.Synthesis and crystallographic study of homeotypic LiVPO4F and LiVPO4O[J].Chemistry of Materials,2012,24(6):1223-1234.
[26]WANG Jie-xi,LI Xin-hai,WANG Zhi-xing,GUO Hua-jun,ZHANG Yun-he,XIONG Xun-hui,HE Zheng-jiang.Synthesis and characterization of LiVPO4F/C using precursor obtained through a soft chemical route with mechanical activation assist[J].Electrochimica Acta,2013,91:75-81.
[27]KIM G H,KIM J H,MYUNG S T,YOON C S,SUN Y K.Improvement of high-voltage cycling behavior of surface-modified Li[Ni1?3Co1?3Mn1?3]O2 cathodes by fluorine substitution for Li-ion batteries[J].Journal of The Electrochemical Society,2005,152(9):A1707-A1713.
[28]张培新,张利,谭智博,任祥忠.Si4+和F-掺杂对Li Ni1/3Co1/3Mn1/3O2结构和电化学性能的影响[J].中国有色金属学报,2011,21(11):2805-2811.ZHANG Pei-xin,ZHANG Li,TAN Zhi-bo,REN Xiang-zhong.Effect of Si4+and F-doping on structure and electrochemical properties of LiNi1/3Co1/3Mn1/3O2[J].The Chinese Journal of Nonferrous Metals,2011,21(11):2805-2811.
[29]SU Li-wei,JING Yu,ZHOU Zhen.Li ion battery materials with core-shell nanostructures[J].Nanoscale,2011,3(10):3967-3983.
[30]曹亮,王安安,艾立华,贾明,刘业翔.石墨烯在锂离子电池材料性能优化中的应用[J].中国有色金属学报,2016,26(4):807-820.CAO Liang,WANG An-an,AI Li-hua,JIA Ming,LIU Ye-xiang.Application of grapheme in performance optimization of lithium ion battery materials[J].The Chinese Journal of Nonferrous Metals,2016,26(4):807-820.
[2]ZAGHIB K,MAUGER A,GROULT H,GOODENOUGH J B,JULIEN C M.Advanced electrodes for high power Li-ion batteries[J].Materials,2013,6(3):1028-1049.
[3]CHERNOVA N A,ROPPOLO M,DILLON A C,WHITTINGHAM M S.Layered vanadium and molybdenum oxides:batteries and electrochromics[J].Journal of Materials Chemistry,2009,19(17):2526-2552.
[4]THAPA A K.Development of cathode materials for Li-ion battery and megalo-capacitance capacitor[D].Saga:Saga University,2007.
[5]XU Bo,QIAN Dan-na,WANG Zi-ying,MENG Y S.Recent progress in cathode materials research for advanced lithium ion batteries[J].Materials Science and Engineering,2012,73(5):51-65.
[6]HE Ping,YU Hai-jun,LI De,ZHOU Hao-shen.Layered lithium transition metal oxide cathodes towards high energy lithium-ion batteries[J].Journal of Materials Chemistry,2012,22(9):3680-3695.
[7]LIU W,OH P L,LIU X,LEE M J,CHO W G,CHAE S J,KIMY S,CHO J P.Nickel-rich layered lithium transition-metal oxide for high-energy lithium‐ion batteries[J].Angewandte Chemie International Edition,2015,54(15):4440-4457.
[8]CHEN Jia-jun.Recent progress in advanced materials for lithium ion batteries[J].Materials,2013,6(1):156-183.
[9]PAN A Q,CHOI D,ZHANG J G,LIANG S Q,CAO G Z,NIE ZM,AREY B W,LIU J.High-rate cathodes based on Li3V2(PO4)3nanobelts prepared via surfactant-assisted fabrication[J].Journal of Power Sources,2011,196(7):3646-3649.
[10]PAN An-qiang,LIU Jun,ZHANG Ji-gang,XU Wu,CAOGuo-zhong,NIE Zi-min,AREY B W,LIANG Shu-quan.Nano-structured Li3V2(PO4)3/carbon composite for high-rate lithium-ion batteries[J].Electrochemistry Communications,2010,12(12):1674-1677.
[11]YIN S C,STROBEL P S,GRONDEY H,NAZAR L F.Li2.5V2(PO4)3:A room-temperature analogue to the fast-ion conducting high-temperatureγ-phase of Li3V2(PO4)3[J].Chemistry of Materials,2004,16(8):1456-1465.
[12]BARKER J,SAIDI M Y,SWOYER J L.Electrochemical insertion properties of the novel lithium vanadium fluorophosphate,LiVPO4F[J].Journal of the Electrochemical Society,2003,150(10):A1394-A1398.
[13]GOVER R K B,BURNS P,BRYAN A,SAIDI S Y,SWOYER JL,BARKER J.LiVPO4F:A new active material for safe lithium-ion batteries[J].Solid State Ionics,2006,177(26):2635-2638.
[14]WANG Jie-xi,WANG Zhi-xing,Ll Xin-hai,GUO Hua-jun,XUXian-wen,ZHANG Xiao-ping,XIAO Wei.x Li3V2(PO4)3·LiVPO4F/C composite cathode materials for lithium ion batteries[J].Electrochimica Acta,2013,87:224-229.
[15]WANG Ren-heng,XIAO Shun-hua LI Xin-hai,WANG Jie-xi,GUO Hua-jun,ZHONG Fu-xin.Structural and electrochemical performance of Na-doped Li3V2(PO4)3/C cathode materials for lithium-ion batteries via rheological phase reaction[J].Journal of Alloys and Compounds,2013,575:268-272.
[16]LIU Zhao-meng,PENG Wen-jie,SHIH Kai-min,WANG Jie-xi,WANG Zhi-xing,GUO Hua-jun,YAN Guo-chun,LI Xin-hai,SONG Liu-bin.A MoS2 coating strategy to improve the comprehensive electrochemical performance of LiVPO4F[J].Journal of Power Sources,2016,315:294-301.
[17]LIM H H,CHO A R,SIVAKUMAR N,KIM W S,YOON W S,LEE Y S.Improved rate capability of Li/Li3V2(PO4)3 cell for advanced lithium secondary battery[J].Bulletin of Korean Chemical Society,2011,32:1491-1494.
[18]BARKER J,GOVER R K B,BURNS P,BRYAN A,SAIDI M Y,SWOYER J L.Structural and electrochemical properties of lithium vanadium fluorophosphate,LiVPO4F[J].Journal of Power Sources,2005,146:516-520.
[19]WU Ling,LU Jia-jia,ZHONG Sheng-kui.Studies of x Li Fe PO4·y Li3V2(PO4)3/C composite cathode materials with high tap density and high performance prepared by sol spray drying method[J].Journal of Solid State Electrochemistry,2013,17(8):2235-2241.
[20]QIN Lai-fen,XIA Yong-gao,QIU Bao,CAO Hai-liang,LIUYuan-zhuang,LIU Zhao-ping.Synthesis and electrochemical performances of(1-x)LiMnPO4·x Li3V2(PO4)3/C composite cathode materials for lithium ion batteries[J].Journal of Power Sources,2013,239:144-150.
[21]LIN Y C,FEY G T K,WU P J,CHANG J K,KAO H M.Synthesis and electrochemical properties of x Li Fe PO4·(1-x)LiVPO4F composites prepared by aqueous precipitation and carbothermal reduction[J].Journal of Power Sources,2013,244:63-71.
[22]ZHANG Bao,SHEN Chao,ZHENG Jun-chao,HAN Ya-dong,ZHANG Jia-feng,MING Lei,WANG Jian-long,QIN Sha-ne,LIHui.Synthesis and characterization of a multi-layer core-shell composite cathode material LiVOPO4-Li3V2(PO4)3[J].Journal of The Electrochemical Society,2014,161(5):A748-A752.
[23]HUANG Huan,YIN S C,KERR T,TAYLOR N,NAZAR L F.Nanostructured composites:A high capacity,fast rate Li3V2(PO4)3/carbon cathode for rechargeable lithium batteries[J].Advanced Materials,2002,14(21):1525-1528.
[24]FEY G T K,LU T L,WU F Y,LI W H.Carboxylic acid-assisted solid-state synthesis of LiFePO4/C composites and their electrochemical properties as cathode materials for lithium-ion batteries[J].Journal of Solid State Electrochemistry,2008,12(7/8):825-833.
[25]ATEBA MBA J M,MASQUELIER C,SUARD E,CROGUENNEC L.Synthesis and crystallographic study of homeotypic LiVPO4F and LiVPO4O[J].Chemistry of Materials,2012,24(6):1223-1234.
[26]WANG Jie-xi,LI Xin-hai,WANG Zhi-xing,GUO Hua-jun,ZHANG Yun-he,XIONG Xun-hui,HE Zheng-jiang.Synthesis and characterization of LiVPO4F/C using precursor obtained through a soft chemical route with mechanical activation assist[J].Electrochimica Acta,2013,91:75-81.
[27]KIM G H,KIM J H,MYUNG S T,YOON C S,SUN Y K.Improvement of high-voltage cycling behavior of surface-modified Li[Ni1?3Co1?3Mn1?3]O2 cathodes by fluorine substitution for Li-ion batteries[J].Journal of The Electrochemical Society,2005,152(9):A1707-A1713.
[28]张培新,张利,谭智博,任祥忠.Si4+和F-掺杂对Li Ni1/3Co1/3Mn1/3O2结构和电化学性能的影响[J].中国有色金属学报,2011,21(11):2805-2811.ZHANG Pei-xin,ZHANG Li,TAN Zhi-bo,REN Xiang-zhong.Effect of Si4+and F-doping on structure and electrochemical properties of LiNi1/3Co1/3Mn1/3O2[J].The Chinese Journal of Nonferrous Metals,2011,21(11):2805-2811.
[29]SU Li-wei,JING Yu,ZHOU Zhen.Li ion battery materials with core-shell nanostructures[J].Nanoscale,2011,3(10):3967-3983.
[30]曹亮,王安安,艾立华,贾明,刘业翔.石墨烯在锂离子电池材料性能优化中的应用[J].中国有色金属学报,2016,26(4):807-820.CAO Liang,WANG An-an,AI Li-hua,JIA Ming,LIU Ye-xiang.Application of grapheme in performance optimization of lithium ion battery materials[J].The Chinese Journal of Nonferrous Metals,2016,26(4):807-820.
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