正极材料聚阴离子型硅酸亚铁锂的研究进展
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摘要
介绍了硅酸亚铁锂(Li2FeSiO4)的结构与充放电机理;综述了Li2FeSiO4的合成方法,如高温固相法、溶胶-凝胶法、自蔓延燃烧法、微波法、熔融盐法、喷雾热解法和水热(溶剂热)法等,并比较了优缺点;探讨了改善该类正极材料电化学性能的途径(碳包覆和离子掺杂等);对发展趋势进行了展望。
The structure and charge-discharge mechanism of lithium iron silicate( Li 2 FeSiO 4) were introduced. The synthesis methods of Li 2 FeSiO 4 were summarized,such as high temperature solid state method,sol-gel method,self-propagating combustion method,microwave method,molten salt method,spray pyrolysis method and hydrothermal( solvothermal) method,their advantages and disadvantages were compared. The ways to improve electrochemical performance of this kind of cathode material such as carbon coating and onic doping were discussed. An insight into the research trends was outlined.
The structure and charge-discharge mechanism of lithium iron silicate( Li 2 FeSiO 4) were introduced. The synthesis methods of Li 2 FeSiO 4 were summarized,such as high temperature solid state method,sol-gel method,self-propagating combustion method,microwave method,molten salt method,spray pyrolysis method and hydrothermal( solvothermal) method,their advantages and disadvantages were compared. The ways to improve electrochemical performance of this kind of cathode material such as carbon coating and onic doping were discussed. An insight into the research trends was outlined.
引文
[1]HUANG Feng-tao(黄锋涛),XU Dan(徐丹),SHU Jie(舒洁),et al.锂离子电池正极材料Li2MSiO4的研究进展[J].Battery Bimonthly(电池),2011,41(3):165-167.
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[17]Zhou H,Einarsrud M A,Vullum-Bruer F.PVA-assisted combustion synthesis and characterization of porous nanocomposite Li2FeSiO4/C[J].Solid State Ionic,2012,225:585-589.
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[19]HU Guo-rong(胡国荣),CAO Yan-bing(曹雁冰),PENG Zhongdong(彭忠东),et al.微波合成法制备锂离子电池正极材料Li2FeSiO4[J].Acta Physico-Chimica Sinica(物理化学学报).2009,25(5):1 004-1 008.
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[21]Huang B,Zheng X,Lu M.Synthesis and electrochemical properties of carbon nano-tubes modified spherical Li2FeSiO4cathode material for lithium-ion batteries[J].J Alloy Compd,2012,525:110-113.
[22]Zhang M,Chen Q,Xi Z,et al.One-step hydrothermal synthesis of Li2FeSiO4/C composites as lithium-ion battery cathode materials[J].J Mater Sci,2012,47(5):2 328-2 332.
[23]Gong Z L,Li Y X,He G N,et al.Nanostructured Li2FeSiO4electrode material synthesized through hydrothermal-assisted sol-gelprocess[J].Electrochem Solid State Lett,2008,11(5):A60-A63.
[24]Rangappa D,Murukanahally K D,Tomai T,et al.Ultrathin nanosheets of Li2MSiO4(M=Fe,Mn)as high-capacity Li-ion battery electrode[J].Nano Lett,2012,12(3):1 146-1 151.
[25]YAN Zi-peng(燕子鹏),CAI Shu(蔡舒),ZHOU Xing(周幸),et al.正极材料纳米Li2FeSiO4/C的溶胶-凝胶法合成及电化学性能[J].Journal of the Chinese Ceramic Society(硅酸盐学报),2012,40(2):734-738.
[26]Guo H J,Cao X A,Li X Q,Li L M,et al.Optimum synthesis of Li2Fe1-x Mn x SiO4/C cathode for lithium ion batteries[J].Electrochim Acta,2010,55(27):8 036-8 042.
[27]Hao H,Wang J,Liu J,et al.Synthesis,characterization and electrochemical performance of Li2FeSiO4/C cathode materials doped by vanadium at Fe/Si sites for lithium ion batteries[J].J Power Sources,2012,210:397-401.
[28]Zhang S,Deng C,Fu B L,et al.Doping effects of magnesium on the electrochemical performance of Li2FeSiO4for lithium ion batteries[J].J Electroanal Chem,2010,644(2):150-154.
[29]Huang X,Chen H,Zhou S,et al.Synthesis and characterization of nano-Li1.95FeSiO4/C composite as cathode material for lithium-ion batteries[J].Electrochim Acta,2012,60:239-243.
[30]Armand M,Tarascon J M,Arroyo-de Dompablo M E.Comparative computational investigation of N and F substituted polyoxoanionic compounds:the case of Li2FeSiO4electrode material[J].Electrochem Commun,2011,13(10):1 047-1 050.
[2]Arroyo-de Dompablo M E,Armand M,Tarascon J M,et al.On-demand design of polyoxianionic cathode materials based on electronegativity correlations:an exploration of the Li2MSiO4system(M=Fe,Mn,Co,Ni)[J].Electrochem Commun,2006,8(8):1 292-1 298.
[3]Dominko R.Li2MSiO4(M=Fe and/or Mn)cathode materials[J].J Power Sources,2008,184(2):462-468.
[4]Nytén A,Abouimrane A,Armand M,et al.Electrochemical performance of Li2FeSiO4as a new Li-battery cathode material[J].Electrochem Commun,2005,7(2):156-160.
[5]Nishimura S I,Hayase S,Kanno R,et al.Structure of Li2FeSiO4[J].J Am Chem Soc,2008,130(40):13 212-13 213.
[6]Sirisopanaporn C,Masquelier C,Bruce P G,et al.Dependence of Li2FeSiO4electrochemistry on structure[J].J Am Chem Soc,2011,133(5):1 263-1 265.
[7]de Dompablo M,Gallardo-Amores J M,Garcia-Martinez J,et al.Is it possible to prepare olivine-type LiFeSiO4?A joint computational and experimental investigation[J].Solid State Ion,2008,179(27-32):1 758-1 762.
[8]Armstrong A R,Kuganathan N,Islam M S,et al.Structure and lithium transport pathways in Li2FeSiO4cathodes for lithium batteries[J].J Am Chem Soc,2011,133(33):13 031-13 035.
[9]Islam M S,Driscoll D J,Fisher C,et al.Atomic-scale investigation of defects,dopants,and lithium transport in the LiFePO4olivinetype battery material[J].Chem Mater,2005,17(20):5 085-5 092.
[10]Zhang P,Hu C H,Wu S Q,et al.Structural properties and energetics of Li2FeSiO4polymorphs and their delithiated products from first-principles[J].Phys Chem Chem Phys,2012,14(20):7 346-7 351.
[11]Sirisopanaporn C,Masquelier C,Bruce P G,et al.Dependence of Li2FeSiO4electrochemistry on structure[J].J Am Chem Soc,2011,133(5):1 263-1 265.
[12]Seo D H,Kim H,Park I,et al.Polymorphism and phase transformations of Li2-x FeSiO4(0
[14]Deng C,Zhang S,Fu B L,et al.Characterization of Li2MnSiO4and Li2FeSiO4cathode materials synthesized via a citric acid assisted sol-gel method[J].Mater Chem Phys,2010,120(1):14-17.
[15]Wu X,Jiang X,Huo Q,et al.Facile synthesis of Li2FeSiO4/C composites with triblock copolymer P123 and their application as cathode materials for lithium ion batteries[J].Electrochim Acta,2012,80:50-55.
[16]Dahbi M,Urbonaite S,Gustafsson T.Combustion synthesis and electrochemical performance of Li2FeSiO4/C cathode material for lithium-ion batteries[J].J Power Sources,2012,205:456-462.
[17]Zhou H,Einarsrud M A,Vullum-Bruer F.PVA-assisted combustion synthesis and characterization of porous nanocomposite Li2FeSiO4/C[J].Solid State Ionic,2012,225:585-589.
[18]Peng Z D,Cao Y B,Hu G R,et al.Microwave synthesis of Li2FeSiO4cathode materials for lithium-ion batteries[J].Chin Chem Lett,2009,20(8):1 000-1 004.
[19]HU Guo-rong(胡国荣),CAO Yan-bing(曹雁冰),PENG Zhongdong(彭忠东),et al.微波合成法制备锂离子电池正极材料Li2FeSiO4[J].Acta Physico-Chimica Sinica(物理化学学报).2009,25(5):1 004-1 008.
[20]Kojima T,Kojima A,Miyuki T,et al.Synthesis method of the Liion battery cathode material Li2FeSiO4using a molten carbonate flux[J].J Electrochem Soc,2011,158(12):A1 340-A1 346.
[21]Huang B,Zheng X,Lu M.Synthesis and electrochemical properties of carbon nano-tubes modified spherical Li2FeSiO4cathode material for lithium-ion batteries[J].J Alloy Compd,2012,525:110-113.
[22]Zhang M,Chen Q,Xi Z,et al.One-step hydrothermal synthesis of Li2FeSiO4/C composites as lithium-ion battery cathode materials[J].J Mater Sci,2012,47(5):2 328-2 332.
[23]Gong Z L,Li Y X,He G N,et al.Nanostructured Li2FeSiO4electrode material synthesized through hydrothermal-assisted sol-gelprocess[J].Electrochem Solid State Lett,2008,11(5):A60-A63.
[24]Rangappa D,Murukanahally K D,Tomai T,et al.Ultrathin nanosheets of Li2MSiO4(M=Fe,Mn)as high-capacity Li-ion battery electrode[J].Nano Lett,2012,12(3):1 146-1 151.
[25]YAN Zi-peng(燕子鹏),CAI Shu(蔡舒),ZHOU Xing(周幸),et al.正极材料纳米Li2FeSiO4/C的溶胶-凝胶法合成及电化学性能[J].Journal of the Chinese Ceramic Society(硅酸盐学报),2012,40(2):734-738.
[26]Guo H J,Cao X A,Li X Q,Li L M,et al.Optimum synthesis of Li2Fe1-x Mn x SiO4/C cathode for lithium ion batteries[J].Electrochim Acta,2010,55(27):8 036-8 042.
[27]Hao H,Wang J,Liu J,et al.Synthesis,characterization and electrochemical performance of Li2FeSiO4/C cathode materials doped by vanadium at Fe/Si sites for lithium ion batteries[J].J Power Sources,2012,210:397-401.
[28]Zhang S,Deng C,Fu B L,et al.Doping effects of magnesium on the electrochemical performance of Li2FeSiO4for lithium ion batteries[J].J Electroanal Chem,2010,644(2):150-154.
[29]Huang X,Chen H,Zhou S,et al.Synthesis and characterization of nano-Li1.95FeSiO4/C composite as cathode material for lithium-ion batteries[J].Electrochim Acta,2012,60:239-243.
[30]Armand M,Tarascon J M,Arroyo-de Dompablo M E.Comparative computational investigation of N and F substituted polyoxoanionic compounds:the case of Li2FeSiO4electrode material[J].Electrochem Commun,2011,13(10):1 047-1 050.