锂离子电池正极材料钒改性聚阴离子型化合物的研究进展
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摘要
聚阴离子型化合物(LiMXOm,M=Fe、Mn、Co、Ni,X=P、Si、S、B、Ti)具有结构稳定、安全性能好等特点,被认为是一种较理想的动力锂离子电池正极材料,但较低的本征电导率严重限制了其实际应用.钒改性可以有效地改善聚阴离子型正极材料的电化学性能,而钒改性方法、钒的用量以及钒的多种价态等造成钒的存在形式复杂多变,分析困难,目前有关钒改性的作用机理仍不清楚.本文简要介绍了钒改性的主要方式,详细综述了钒改性聚阴离子型正极材料磷酸铁锂和硅酸铁锂的研究现状,讨论了钒改性和钒表征的难点,指出了今后该领域的研究方向.
Polyanionic compounds(LiMXOm,M=Fe,Mn,Co,Ni,X=P,Si,S,B,Ti)have been considered as one of the most promising cathode materials for power lithium ion batteries because of their excellent structural stability,good reliability,and high performance.However,low intrinsic electrical conductivity has limited their practical applications.Vanadium modifications have been shown to significantly improve the electrochemical performance of the polyanion-type cathode materials.The methods used for vanadium modifications,the amounts and diversified valence states of vanadium,as well as the difficulties in vanadium identifications,result in the complexities and varieties of vanadium existing forms.Accordingly,the mechanisms of vanadium modifications remain unclear.In this paper,basic forms of vanadium modifications are briefly introduced,and recent progress in vanadium modified polyaniontype cathode materials,such as LiFePO4 and Li2FeSiO4,is reviewed in detail.The difficulties involved in vanadium modifications and identifications in vanadium modified polyanionic compounds are also discussed.Future research trends in the field of vanadium modified polyanion-type cathode materials for lithium ion batteries are highlighted.
Polyanionic compounds(LiMXOm,M=Fe,Mn,Co,Ni,X=P,Si,S,B,Ti)have been considered as one of the most promising cathode materials for power lithium ion batteries because of their excellent structural stability,good reliability,and high performance.However,low intrinsic electrical conductivity has limited their practical applications.Vanadium modifications have been shown to significantly improve the electrochemical performance of the polyanion-type cathode materials.The methods used for vanadium modifications,the amounts and diversified valence states of vanadium,as well as the difficulties in vanadium identifications,result in the complexities and varieties of vanadium existing forms.Accordingly,the mechanisms of vanadium modifications remain unclear.In this paper,basic forms of vanadium modifications are briefly introduced,and recent progress in vanadium modified polyaniontype cathode materials,such as LiFePO4 and Li2FeSiO4,is reviewed in detail.The difficulties involved in vanadium modifications and identifications in vanadium modified polyanionic compounds are also discussed.Future research trends in the field of vanadium modified polyanion-type cathode materials for lithium ion batteries are highlighted.
引文
[1]Yang J L,Kang X C,Hu L,et al.NanocrystallineLi2FeSiO4synthesized by carbon frameworks as an advanced cathode material for Li-ion batteries[J].Journal of Materials Chemistry A,2014,2(19):6870-6878.
[2]Zhang L L,Duan S,Yang X L,et al.Systematic investigation on Cadmium-incorporation in Li2FeSiO4/C cathode material for lithium-ion batteries[J].Scientific Reports,2014,4:5064.
[3]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].Electrochemistry Communications,2011,13(10):1047-1050.
[4]Chen Z X,Qiu S,Cao Y L,et al.Hierarchical porous Li2FeSiO4/C composite with 2 Li storage capacity and long cycle stability for advanced Li-ion batteries[J].Journal of Materials Chemistry A,2013,1(16):4988-4992.
[5]Kellerman D G,Chukalkin Y G,Medvedeva N L,et al.Hydrogen reduction of vanadium in vanadium-doped LiMnPO4[J].Materials Chemistry and Physics,2015,149,150:209-215.
[6]Zhao R R,Hung I M,Li Y T,et al.Synthesis and properties of Co-doped LiFePO4as cathode material via a hydrothermal route for lithium-ion batteries[J].Journal of Alloys and Compounds,2012,513:282-288.
[7]Gao K.Effect of Mn doping on electrochemical properties of Li2FeSiO4/C cathode materials based on a vacuum solid-state method[J].Ionics,2014,20(6):809-815.
[8]Deng C,Zhang S,Yang S Y,et al.Synthesis and characterization of Li2Fe0.97 M0.03SiO4(M=Zn2+,Cu2+,Ni 2+)cathode materials for lithium ion batteries[J].Journal of Power Sources,2011,196(1):386-392.
[9]Talebi-Esfandarani M,Savadogo O.Enhancement of electrochemical properties of platinum doped LiFePO4/C cathode material synthesized using hydrothermal method[J].Solid State Ionics,2014,261:81-86.
[10]Deng C,Zhang S,Wu Y X,et al.Partial substitution of Mn/Si with V,Cr or Al in Li2MnSiO4 nanoparticle:dependence of the physical and electrochemical properties on the substitution strategy[J].Journal of Electroanalytical Chemistry,2014,719:150-157.
[11]Hu C W,Chen T Y,Shih K S,et al.Real-time investigation on the influences of vanadium additives to the structural and chemical state evolutions of LiFePO4for enhancing the electrochemical performance of lithium-ion battery[J].Journal of Power Sources,2014,270:449-456.
[12]Lin H,Wen Y W,Zhang C X,et al.A GGA+U study of lithium diffusion in vanadium doped LiFePO4[J].Solid State Communications,2012,152(12):999-1003.
[13]Chiang C Y,Su H C,Wu P J,et al.Vanadium substitution of LiFePO4cathode materials to enhance the capacity of LiFePO4-based lithium-ion batteries[J].The Journal of Physical Chemistry C,2012,116(46):24424-24429.
[14]文衍宣,郑绵平,童张法.锂离子蓄电池正极材料LiVxFe1-xPO4的制备和性能[J].电源技术,2005,29(11):713-715.
[15]Wen Y X,Zeng L M,Tong Z F,et al.Structure and properties of LiFe0.9V0.1PO4[J].Journal of Alloys and Compounds,2006,416(1/2):206-208.
[16]Hong J,Wang C S,Chen X,et al.Vanadium modified LiFePO4cathode for Li-ion batteries[J].Electrochemical and Solid-State Letters,2009,12(2):A33-A38.
[17]Zhao T,Xu W,Ye Q,et al.Local structure of vanadium in doped LiFePO4[J].J Synchrotron Radiat,2010,17(5):584-589.
[18]Harrison K L,Manthiram A.Microwave-assisted solvothermal synthesis and characterization of metastable LiFe1-x(VO)xPO4 Cathodes[J].Inorganic Chemistry,2011,50(8):3613-3620.
[19]Sun C S,Zhou Z,Xu Z G,et al.Improved high-rate charge/discharge performances of LiFePO4/C via V-doping[J].Journal of Power Sources,2009,193(2):841-845.
[20]Ma J,Li B,Du H,et al.The Effect of vanadium on physicochemical and electrochemical performances of LiFePO4cathode for lithium battery[J].Journal of The Electrochemical Society,2011,158(1):A26-A32.
[21]Zhang L L,Liang G,Ignatov A,et al.Effect of vanadium incorporation on electrochemical performance of LiFePO4for lithium-ion batteries[J].The Journal of Physical Chemistry C,2011,115(27):13520-13527.
[22]Omenya F,Chernova N A,Upreti S,et al.Can vanadium be substituted into LiFePO4[J].Chemistry of Materials,2011,23(21):4733-4740.
[23]李云松.基于硅酸铁锂正极材料的改性研究[D].厦门:厦门大学,2012:9.
[24]Nyten A,Abouimrane A,Armand M,et al.Electrochemical performance of Li2FeSiO4as a new Li-battery cathode material[J].Electrochemistry Communications,2005,7(2):156-160.
[25]Nishimura S,Hayase S,Kanno R,et al.Structure of Li2FeSiO4[J].Journal of the American Chemical Society,2008,130(40):13212-13213.
[26]Sirisopanaporn C,Boulineau A,Hanzel D,et al.Crystal structure of a new polymorph of Li2FeSiO4[J].Inorganic Chemistry,2010,49(16):7446-7451.
[27]Boulineau A,Sirisopanaporn C,Dominko R,et al.Polymorphism and structural defects in Li2FeSiO4[J].Dalton Transactions,2010,39(27):6310-6316.
[28]Li Y S,Cheng X,Zhang Y.Achieving high capacity by vanadium substitution into Li2FeSiO4[J].Journal of the Electrochemical Society,2012,159(2):A69-A74.
[29]Hao H,Wang J B,Liu J L,et al.Synthesis,characterization and electrochemical performance of Li2FeSiO4/C cathode materials doped by vanadium at Fe/Si sites for lithium ion batteries[J].Journal of Power Sources,2012,210:397-401.
[30]Liivat A,Thomas J O.A DFT study of polyanion substitution into the Li-ion battery cathode material Li2FeSiO4[J].Computational Materials Science,2010,50(1):191-197.
[31]Zhang L L,Sun H B,Yang X L,et al.Study on electrochemical performance and mechanism of V-doped Li2FeSiO4cathode material for Li-ion batteries[J].Electrochimica Acta,2015,152:496-504.
[32]Yang H,Zhang Y,Cheng X.Effect of vanadium substitution on structure of Li2FeSiO4/C composites[J].Journal of Electrochemistry,2013,19(6):565-570.
[33]Jin C,Zhang X D,He W,et al.Effect of ion doping on the electrochemical performances of LiFePO4-Li3V2(PO4)3composite cathode materials[J].Rsc Advances,2014,4(30):15332-15339.
[34]Zheng J C,Li X H,Wang Z X,et al.Novel synthesis of LiFePO4-Li3V2(PO4)3composite cathode material by aqueous precipitation and lithiation[J].Journal of Power Sources,2010,195(9):2935-2938.
[35]Xiang J Y,Tu J P,Zhang L,et al.Improved electrochemical performances of 9LiFePO4·Li3V2(PO4)/C composite prepared by a simple solid-state method[J].Journal of Power Sources,2010,195(24):8331-8335.
[36]Chen X J,Cao G S,Zhao X B,et al.Electrochemical performance of LiFe1-xVxPO4/carbon composites prepared by solid-state reaction[J].Journal of Alloys and Compounds,2008,463(1/2):385-389.
[37]Wu L,Lu J J,Zhong S K.Studies of xLiFePO4·yLi3V2(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.
[38]Park K S,Benayad A,Park M S,et al.Tailoring the electrochemical properties of composite electrodes by introducing surface redox-active oxide film:VOx-impregnated LiFePO4electrode[J].Chemical Communications,2010,46(15):2572-2574.
[39]Jin Y,Yang C P,Rui X H,et al.V2O3 modified LiFePO4/C composite with improved electrochemical performance[J].Journal of Power Sources,2011,196(13):5623-5630.
[40]Zhang Y,Shao G J,Ma Z P,et al.Influence of surface modification by vanadium oxide and carbon on the electrochemical performance of LiFePO4/C[J].Ionics,2012,19(8):1091-1097.
[41]Livage J.Vanadium pentoxide gels[J].Chem Mater,1991,3(4):578-593.
[42]Ma J,Li B H,Kang F Y.Improved electrochemical performances of nanocrystalline LiFePO4/C composite cathode via V-doping and VO2(B)coating[J].Journal of Physics and Chemistry of Solids,2012,73(12):1463-1468.
[43]Clemens O,Bauer M,Haberkorn R,et al.Synthesis and characterization of vanadium-doped LiMnPO4 compounds:LiMn(PO4)x(VO4)1-x(0.8≤x≤1.0)[J].Chemistry of Materials,2012,24(24):4717-4724.
[44]Wang Y M,Wang G j,Zhang M l,et al.Preparation and electrochemical performance of V-doped LiCoPO4cathode materials[J].Journal of Functional Materials,2011,4:027.
[45]Deng C,Zhang S,Wu Y X,et al.Partial substitution of Mn/Si with V,Cr or Al in Li2MnSiO4 nanoparticle:dependence of the physical and electrochemical properties on the substitution strategy[J].Journal of Electroanalytical Chemistry,2014,719:150-157.
[46]Wang F,Yang J,NuLi Y N,et al.Composites of LiMnPO4 with Li3V2(PO4)3for cathode in lithium-ion battery[J].Electrochimica Acta,2013,103:96-102.
[47]Wang F,Yang J,NuLi Y N,et al.Highly promoted electrochemical performance of 5V LiCoPO4cathode material by addition of vanadium[J].Journal of Power Sources,2010,195(19):6884-6887.
[2]Zhang L L,Duan S,Yang X L,et al.Systematic investigation on Cadmium-incorporation in Li2FeSiO4/C cathode material for lithium-ion batteries[J].Scientific Reports,2014,4:5064.
[3]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].Electrochemistry Communications,2011,13(10):1047-1050.
[4]Chen Z X,Qiu S,Cao Y L,et al.Hierarchical porous Li2FeSiO4/C composite with 2 Li storage capacity and long cycle stability for advanced Li-ion batteries[J].Journal of Materials Chemistry A,2013,1(16):4988-4992.
[5]Kellerman D G,Chukalkin Y G,Medvedeva N L,et al.Hydrogen reduction of vanadium in vanadium-doped LiMnPO4[J].Materials Chemistry and Physics,2015,149,150:209-215.
[6]Zhao R R,Hung I M,Li Y T,et al.Synthesis and properties of Co-doped LiFePO4as cathode material via a hydrothermal route for lithium-ion batteries[J].Journal of Alloys and Compounds,2012,513:282-288.
[7]Gao K.Effect of Mn doping on electrochemical properties of Li2FeSiO4/C cathode materials based on a vacuum solid-state method[J].Ionics,2014,20(6):809-815.
[8]Deng C,Zhang S,Yang S Y,et al.Synthesis and characterization of Li2Fe0.97 M0.03SiO4(M=Zn2+,Cu2+,Ni 2+)cathode materials for lithium ion batteries[J].Journal of Power Sources,2011,196(1):386-392.
[9]Talebi-Esfandarani M,Savadogo O.Enhancement of electrochemical properties of platinum doped LiFePO4/C cathode material synthesized using hydrothermal method[J].Solid State Ionics,2014,261:81-86.
[10]Deng C,Zhang S,Wu Y X,et al.Partial substitution of Mn/Si with V,Cr or Al in Li2MnSiO4 nanoparticle:dependence of the physical and electrochemical properties on the substitution strategy[J].Journal of Electroanalytical Chemistry,2014,719:150-157.
[11]Hu C W,Chen T Y,Shih K S,et al.Real-time investigation on the influences of vanadium additives to the structural and chemical state evolutions of LiFePO4for enhancing the electrochemical performance of lithium-ion battery[J].Journal of Power Sources,2014,270:449-456.
[12]Lin H,Wen Y W,Zhang C X,et al.A GGA+U study of lithium diffusion in vanadium doped LiFePO4[J].Solid State Communications,2012,152(12):999-1003.
[13]Chiang C Y,Su H C,Wu P J,et al.Vanadium substitution of LiFePO4cathode materials to enhance the capacity of LiFePO4-based lithium-ion batteries[J].The Journal of Physical Chemistry C,2012,116(46):24424-24429.
[14]文衍宣,郑绵平,童张法.锂离子蓄电池正极材料LiVxFe1-xPO4的制备和性能[J].电源技术,2005,29(11):713-715.
[15]Wen Y X,Zeng L M,Tong Z F,et al.Structure and properties of LiFe0.9V0.1PO4[J].Journal of Alloys and Compounds,2006,416(1/2):206-208.
[16]Hong J,Wang C S,Chen X,et al.Vanadium modified LiFePO4cathode for Li-ion batteries[J].Electrochemical and Solid-State Letters,2009,12(2):A33-A38.
[17]Zhao T,Xu W,Ye Q,et al.Local structure of vanadium in doped LiFePO4[J].J Synchrotron Radiat,2010,17(5):584-589.
[18]Harrison K L,Manthiram A.Microwave-assisted solvothermal synthesis and characterization of metastable LiFe1-x(VO)xPO4 Cathodes[J].Inorganic Chemistry,2011,50(8):3613-3620.
[19]Sun C S,Zhou Z,Xu Z G,et al.Improved high-rate charge/discharge performances of LiFePO4/C via V-doping[J].Journal of Power Sources,2009,193(2):841-845.
[20]Ma J,Li B,Du H,et al.The Effect of vanadium on physicochemical and electrochemical performances of LiFePO4cathode for lithium battery[J].Journal of The Electrochemical Society,2011,158(1):A26-A32.
[21]Zhang L L,Liang G,Ignatov A,et al.Effect of vanadium incorporation on electrochemical performance of LiFePO4for lithium-ion batteries[J].The Journal of Physical Chemistry C,2011,115(27):13520-13527.
[22]Omenya F,Chernova N A,Upreti S,et al.Can vanadium be substituted into LiFePO4[J].Chemistry of Materials,2011,23(21):4733-4740.
[23]李云松.基于硅酸铁锂正极材料的改性研究[D].厦门:厦门大学,2012:9.
[24]Nyten A,Abouimrane A,Armand M,et al.Electrochemical performance of Li2FeSiO4as a new Li-battery cathode material[J].Electrochemistry Communications,2005,7(2):156-160.
[25]Nishimura S,Hayase S,Kanno R,et al.Structure of Li2FeSiO4[J].Journal of the American Chemical Society,2008,130(40):13212-13213.
[26]Sirisopanaporn C,Boulineau A,Hanzel D,et al.Crystal structure of a new polymorph of Li2FeSiO4[J].Inorganic Chemistry,2010,49(16):7446-7451.
[27]Boulineau A,Sirisopanaporn C,Dominko R,et al.Polymorphism and structural defects in Li2FeSiO4[J].Dalton Transactions,2010,39(27):6310-6316.
[28]Li Y S,Cheng X,Zhang Y.Achieving high capacity by vanadium substitution into Li2FeSiO4[J].Journal of the Electrochemical Society,2012,159(2):A69-A74.
[29]Hao H,Wang J B,Liu J L,et al.Synthesis,characterization and electrochemical performance of Li2FeSiO4/C cathode materials doped by vanadium at Fe/Si sites for lithium ion batteries[J].Journal of Power Sources,2012,210:397-401.
[30]Liivat A,Thomas J O.A DFT study of polyanion substitution into the Li-ion battery cathode material Li2FeSiO4[J].Computational Materials Science,2010,50(1):191-197.
[31]Zhang L L,Sun H B,Yang X L,et al.Study on electrochemical performance and mechanism of V-doped Li2FeSiO4cathode material for Li-ion batteries[J].Electrochimica Acta,2015,152:496-504.
[32]Yang H,Zhang Y,Cheng X.Effect of vanadium substitution on structure of Li2FeSiO4/C composites[J].Journal of Electrochemistry,2013,19(6):565-570.
[33]Jin C,Zhang X D,He W,et al.Effect of ion doping on the electrochemical performances of LiFePO4-Li3V2(PO4)3composite cathode materials[J].Rsc Advances,2014,4(30):15332-15339.
[34]Zheng J C,Li X H,Wang Z X,et al.Novel synthesis of LiFePO4-Li3V2(PO4)3composite cathode material by aqueous precipitation and lithiation[J].Journal of Power Sources,2010,195(9):2935-2938.
[35]Xiang J Y,Tu J P,Zhang L,et al.Improved electrochemical performances of 9LiFePO4·Li3V2(PO4)/C composite prepared by a simple solid-state method[J].Journal of Power Sources,2010,195(24):8331-8335.
[36]Chen X J,Cao G S,Zhao X B,et al.Electrochemical performance of LiFe1-xVxPO4/carbon composites prepared by solid-state reaction[J].Journal of Alloys and Compounds,2008,463(1/2):385-389.
[37]Wu L,Lu J J,Zhong S K.Studies of xLiFePO4·yLi3V2(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.
[38]Park K S,Benayad A,Park M S,et al.Tailoring the electrochemical properties of composite electrodes by introducing surface redox-active oxide film:VOx-impregnated LiFePO4electrode[J].Chemical Communications,2010,46(15):2572-2574.
[39]Jin Y,Yang C P,Rui X H,et al.V2O3 modified LiFePO4/C composite with improved electrochemical performance[J].Journal of Power Sources,2011,196(13):5623-5630.
[40]Zhang Y,Shao G J,Ma Z P,et al.Influence of surface modification by vanadium oxide and carbon on the electrochemical performance of LiFePO4/C[J].Ionics,2012,19(8):1091-1097.
[41]Livage J.Vanadium pentoxide gels[J].Chem Mater,1991,3(4):578-593.
[42]Ma J,Li B H,Kang F Y.Improved electrochemical performances of nanocrystalline LiFePO4/C composite cathode via V-doping and VO2(B)coating[J].Journal of Physics and Chemistry of Solids,2012,73(12):1463-1468.
[43]Clemens O,Bauer M,Haberkorn R,et al.Synthesis and characterization of vanadium-doped LiMnPO4 compounds:LiMn(PO4)x(VO4)1-x(0.8≤x≤1.0)[J].Chemistry of Materials,2012,24(24):4717-4724.
[44]Wang Y M,Wang G j,Zhang M l,et al.Preparation and electrochemical performance of V-doped LiCoPO4cathode materials[J].Journal of Functional Materials,2011,4:027.
[45]Deng C,Zhang S,Wu Y X,et al.Partial substitution of Mn/Si with V,Cr or Al in Li2MnSiO4 nanoparticle:dependence of the physical and electrochemical properties on the substitution strategy[J].Journal of Electroanalytical Chemistry,2014,719:150-157.
[46]Wang F,Yang J,NuLi Y N,et al.Composites of LiMnPO4 with Li3V2(PO4)3for cathode in lithium-ion battery[J].Electrochimica Acta,2013,103:96-102.
[47]Wang F,Yang J,NuLi Y N,et al.Highly promoted electrochemical performance of 5V LiCoPO4cathode material by addition of vanadium[J].Journal of Power Sources,2010,195(19):6884-6887.