V掺杂Li2FeSiO4正极材料的制备与电化学性能
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摘要
采用固相法制备了V掺杂的锂离子正极材料Li2Fe Si(1–x)VxO4(其中x=0,0.05,0.10,0.15)。通过X射线衍射(XRD)、扫描电子显微镜、粒度分析、恒流充放电测试及交流阻抗谱测试等方法研究制备样品的结构、形貌及电化学性能。结果表明:掺杂后样品的衍射主峰与Li2Fe Si O4的XRD谱一致,样品的一次粒径分布在200~500 nm之间,颗粒分散较为均匀,掺杂后样品的粒度分布更为一致。电学性能测试显示:x=0.10时,样品表现出较好的电学性能。在0.1C下放电,Li2Fe Si0.90V0.10O4的首次放电容量为163 m A·h/g,与Li2Fe Si O4相比容量增加了66.2%,循环30次后的容量仍保持在127m A·h/g,具有良好的循环性能。
Lithium ion cathode materials Li2 Fe Si(1–x)VxO4(x=0, 0.05, 0.10, 0.15) with V doped was synthesized by a solid-state method. The structure, morphology and electrochemical performance of the samples were analyzed by X-ray diffraction(XRD), scanning electron microscopy, particle size analysis, constant current charge–discharge tests and electrochemical impedance spectra measurement, respectively. The results show that the main XRD peak of the Li2 Fe Si(1–x)VxO4 is consistent with the Li2 Fe Si O4, and the primary particle size is between 200–500 nm and the particle size distribution is narrower after doping. The Li2 Fe Si0.90V0.10O4 sample exhibits a better electrochemical performance. The initial specific capacity of the Li2 Fe Si0.90V0.10O4 sample is 163 m A·h/g at 0.1C. Compared to Li2 Fe Si O4, the discharge capacity of the Li2 Fe Si0.90V0.10O4 sample is increased by 66.2%. The capacity is 127 m A·h/g after 30 cycles, showing that the Li2 Fe Si0.90V0.10O4 sample has a good cycle performance.
Lithium ion cathode materials Li2 Fe Si(1–x)VxO4(x=0, 0.05, 0.10, 0.15) with V doped was synthesized by a solid-state method. The structure, morphology and electrochemical performance of the samples were analyzed by X-ray diffraction(XRD), scanning electron microscopy, particle size analysis, constant current charge–discharge tests and electrochemical impedance spectra measurement, respectively. The results show that the main XRD peak of the Li2 Fe Si(1–x)VxO4 is consistent with the Li2 Fe Si O4, and the primary particle size is between 200–500 nm and the particle size distribution is narrower after doping. The Li2 Fe Si0.90V0.10O4 sample exhibits a better electrochemical performance. The initial specific capacity of the Li2 Fe Si0.90V0.10O4 sample is 163 m A·h/g at 0.1C. Compared to Li2 Fe Si O4, the discharge capacity of the Li2 Fe Si0.90V0.10O4 sample is increased by 66.2%. The capacity is 127 m A·h/g after 30 cycles, showing that the Li2 Fe Si0.90V0.10O4 sample has a good cycle performance.
引文
[1]NYTEN A,ABOUIMRANE A,ARMAND M,et al.Electrochemical performance of Li2Fe Si O4 as a new Li-battery cathode material[J].Electrochem Commun,2005,7(2):156-60.
[2]李云松,傅儒生,程璇,等.前驱体固相法制备硅酸铁锂正极材料[J].硅酸盐学报,2011,39(7):1097-1101.LI Yunsong,FU rusheng,CHENG xuan,et al.J Chin Ceram Soc,2011,39(7):1097-1101.
[3]杨金龙,木士春.锂离子电池正极材料硅酸亚铁锂的研究现状[J].电池,2012,42(3):164-167.YANG Jinlong,MU Shichun.Battery Bimonthly(in Chinese),2012,42(3):164-167.
[4]曹璇,郭华军,李向群,等.锂离子电池正极材料Li2Fe Si O4的改性[J].中南大学学报:自然科学版,2012,43(1):23-27.CAO Xuan,GUO Huajun,LI Xiangqun,et al.J Cent South Univ:Sci Technol,2012,43(1):23-27.
[5]向楷雄,陈晗,龚文强.硅酸铁锂的合成及改性研究进展[J].电源技术,2012,36(7):1065-1067.XIANG Kaixiong,CHEN Han,GONG Wenqiang.Chin J Power Sources(in Chinese),2012,36(7):1065-1067.
[6]郭丽彬,李学良.锂离子电池新型正极材料Li2Fe Si O4的研究进展[J].电池工业,2010,15(5):313–320.GUO Libin,LI Xueliang.Chin Battery Ind(in Chinese),2010,15(5):313-320.
[7]范成杰,左晓希,李奇,等.锂离子电池新型阴极材料Li2Fe Si O4的研究进展[J].材料导报A:综述篇,2012,26(2):149-153.FAN Chengjie,ZUO Xiaoxi,LI Qi,et al.Mater Rev A:Rev Article(in Chinese),2012,26(2):149-153.
[8]刘兴亮,鲁道荣,桂宏亮.Co2+掺杂对Li2Fe Si O4/C电化学性能的影响[J].金属功能材料,2013,20(3):16-19.LIU Xingliang,LU Daorong,GUI Hongliang.Met Func Mater(in Chinese),2013,20(3):16–19.
[9]李黎明.锂离子电池正极材料Li2Fe Si O4/C的合成与改性研究[D].长沙:中南大学,2010.LI liming.Study on Synthesis and modification of Li2Fe Si O4/C cathode material for lithium ion batteries(in Chinese,dissertation).Changsha:Central South University,2010.
[10]YANG H,ZHANG Y,CHENG X.Effect of Vanadium Substitution on Structure of Li2Fe Si O4/C Composites[J].J Electrochem,2013,19(6):564-570.
[11]兰建云,赵敏寿,王艳芝,等.Al3+掺杂对Li2Fe Si O4结构和电化学性能影响的研究[J].无机化学学报,2011,27(8):1497–1502.LAN Jianyun,ZHAO Minshou,WANG Yanzhi,et al.Chin J Inorg Chem(in Chinese),2011,27(8):1497-1502.
[12]SHAO B,TANIGUCHI I.Synthesis of Li2Fe Si O4/C nanocomposite cathodes for lithium batteries by a novel synthesis route and their electrochemical properties[J].J Power Sources,2012,199(2):278-286.
[13]YAN Z P,CAI S,MIAO L J,et al.Synthesis and characterization of in situ carbon-coated Li2Fe Si O4 cathode materials for lithium ion battery[J].J Alloy Compd,2012,511(1):101-106.
[14]伍仁强,陈梅蓉,韩铭,等.掺铌硅酸亚铁锂正极材料的电化学性能[J].吉林化工学院学报,2012,29(3):1-5.WU Renqiang,CHEN Meirong,HAN Ming,et al.Jilin Inst Chem Technol(in Chinese),2012,29(3):1-5.
[15]PENG G,ZHANG LL,YANG XL,et al.Enhanced electrochemical performance of multi-walled carbon nanotubes modified Li2Fe Si O4/C cathode material for lithium-ion batteries[J].J Alloy Compd,2013,570(9):1-6.
[16]王毅,高飞飞,李影,等.钒掺杂对正极材料Li Fe PO4/C性能的影响[J].电池,2010,40(6):310-312.WANG Yi,GAO Feifei,LI Ying,et al.Battery Bimonthly(in Chinese),2010,40(6):310-312.
[17]HUA N,WANG CY,KANG XY,et al.Studies of V doping for the Li Fe PO4-based Li Ion batteries[J].J Alloy Compd,2010,503(1):204-208.
[18]蒿豪.锂离子电池正极材料Li2Fe Si O4/C的合成与改性研究[D].上海:复旦大学,2012.HAO Hao.Study on Synthesis and modification of Li2Fe Si O4/C cathode material for lithium ion batteries(in Chinese,dissertation),Shanghai:Fudan University,2012..
[2]李云松,傅儒生,程璇,等.前驱体固相法制备硅酸铁锂正极材料[J].硅酸盐学报,2011,39(7):1097-1101.LI Yunsong,FU rusheng,CHENG xuan,et al.J Chin Ceram Soc,2011,39(7):1097-1101.
[3]杨金龙,木士春.锂离子电池正极材料硅酸亚铁锂的研究现状[J].电池,2012,42(3):164-167.YANG Jinlong,MU Shichun.Battery Bimonthly(in Chinese),2012,42(3):164-167.
[4]曹璇,郭华军,李向群,等.锂离子电池正极材料Li2Fe Si O4的改性[J].中南大学学报:自然科学版,2012,43(1):23-27.CAO Xuan,GUO Huajun,LI Xiangqun,et al.J Cent South Univ:Sci Technol,2012,43(1):23-27.
[5]向楷雄,陈晗,龚文强.硅酸铁锂的合成及改性研究进展[J].电源技术,2012,36(7):1065-1067.XIANG Kaixiong,CHEN Han,GONG Wenqiang.Chin J Power Sources(in Chinese),2012,36(7):1065-1067.
[6]郭丽彬,李学良.锂离子电池新型正极材料Li2Fe Si O4的研究进展[J].电池工业,2010,15(5):313–320.GUO Libin,LI Xueliang.Chin Battery Ind(in Chinese),2010,15(5):313-320.
[7]范成杰,左晓希,李奇,等.锂离子电池新型阴极材料Li2Fe Si O4的研究进展[J].材料导报A:综述篇,2012,26(2):149-153.FAN Chengjie,ZUO Xiaoxi,LI Qi,et al.Mater Rev A:Rev Article(in Chinese),2012,26(2):149-153.
[8]刘兴亮,鲁道荣,桂宏亮.Co2+掺杂对Li2Fe Si O4/C电化学性能的影响[J].金属功能材料,2013,20(3):16-19.LIU Xingliang,LU Daorong,GUI Hongliang.Met Func Mater(in Chinese),2013,20(3):16–19.
[9]李黎明.锂离子电池正极材料Li2Fe Si O4/C的合成与改性研究[D].长沙:中南大学,2010.LI liming.Study on Synthesis and modification of Li2Fe Si O4/C cathode material for lithium ion batteries(in Chinese,dissertation).Changsha:Central South University,2010.
[10]YANG H,ZHANG Y,CHENG X.Effect of Vanadium Substitution on Structure of Li2Fe Si O4/C Composites[J].J Electrochem,2013,19(6):564-570.
[11]兰建云,赵敏寿,王艳芝,等.Al3+掺杂对Li2Fe Si O4结构和电化学性能影响的研究[J].无机化学学报,2011,27(8):1497–1502.LAN Jianyun,ZHAO Minshou,WANG Yanzhi,et al.Chin J Inorg Chem(in Chinese),2011,27(8):1497-1502.
[12]SHAO B,TANIGUCHI I.Synthesis of Li2Fe Si O4/C nanocomposite cathodes for lithium batteries by a novel synthesis route and their electrochemical properties[J].J Power Sources,2012,199(2):278-286.
[13]YAN Z P,CAI S,MIAO L J,et al.Synthesis and characterization of in situ carbon-coated Li2Fe Si O4 cathode materials for lithium ion battery[J].J Alloy Compd,2012,511(1):101-106.
[14]伍仁强,陈梅蓉,韩铭,等.掺铌硅酸亚铁锂正极材料的电化学性能[J].吉林化工学院学报,2012,29(3):1-5.WU Renqiang,CHEN Meirong,HAN Ming,et al.Jilin Inst Chem Technol(in Chinese),2012,29(3):1-5.
[15]PENG G,ZHANG LL,YANG XL,et al.Enhanced electrochemical performance of multi-walled carbon nanotubes modified Li2Fe Si O4/C cathode material for lithium-ion batteries[J].J Alloy Compd,2013,570(9):1-6.
[16]王毅,高飞飞,李影,等.钒掺杂对正极材料Li Fe PO4/C性能的影响[J].电池,2010,40(6):310-312.WANG Yi,GAO Feifei,LI Ying,et al.Battery Bimonthly(in Chinese),2010,40(6):310-312.
[17]HUA N,WANG CY,KANG XY,et al.Studies of V doping for the Li Fe PO4-based Li Ion batteries[J].J Alloy Compd,2010,503(1):204-208.
[18]蒿豪.锂离子电池正极材料Li2Fe Si O4/C的合成与改性研究[D].上海:复旦大学,2012.HAO Hao.Study on Synthesis and modification of Li2Fe Si O4/C cathode material for lithium ion batteries(in Chinese,dissertation),Shanghai:Fudan University,2012..