锂离子电池电极材料磷酸氧钒锂的研究进展

doi:10.3724/SP.J.1095.2014.30632

摘要/Abstract

摘要： 介绍了磷酸氧钒锂（α-LiVOPO4、β-LiVOPO4和αⅠ-LiVOPO4）电极材料的结构和电化学性能；综述了现有的LiVOPO4电极材料的合成方法(包括高温固相法，化学还原法，溶胶-凝胶法，溶剂热法，离子交换法等)及其改性研究现状。最后对其未来的发展趋势进行了展望。

关键词: 锂离子电池, 磷酸氧钒锂, 正极材料, 合成方法

Abstract: The structures and electrochemical performance of lithium vanadyl phosphate(α-LiVOPO4, β-LiVOPO4 and αⅠ-LiVOPO4) were presented. High temperature solid state, chemical reduction, sol-gel, solvothermal and ion exchange methods for the synthesis of LiVOPO4 were reviewed. The modification research status of LiVOPO4 was summarized in brief. Finally the prospect of application tendency was depicted.

Key words: lithium ion batteries, lithium vanadyl phosphate, cathode materials, synthetic methods

中图分类号:

O646.2

贺冬华, 唐安平, 申洁, 徐国荣, 刘立华, 令玉林. 锂离子电池电极材料磷酸氧钒锂的研究进展[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30632.

HE Donghua1, TANG Anping1,2*, SHEN Jie1, XU Guorong1,2, LIU Lihua1,2, LING Yuling1,2. Progress in Lithium Vanadyl Phosphate as Electrode Materials for Lithium Ion Batteries[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30632.

参考文献

[1] Yamada A,Chung S C,Hinokuma K. Optimized LiFePO4 for Lithium Battery Cathodes[J]. J Electrochem Soc,2001,148(3):224-229.

[2] Huang H,Yin S C,Nazar L F. Approaching Theoretical Capacity of LiFePO4 at Room Temperature at High Rates[J]. Electrochem Solid-State Lett,2001,4(10):170-172.

[3] Takahashi M,Tobishima S I,Takei K J,et al. Reaction Behavior of LiFePO4 as a Cathode Material for Rechargeable Lithium Batteries[J]. Solid State Ionics,2002,148:283-289.

[4] Hsu K F,Tsaya S Y,Hwang B G. Synthesis and Characterization of Nano-sized LiFePO4 Cathode Materials Prepared by a Citric Aacid-based Sol gel Route[J]. J Mater Chem,2004,14:2690-2695.

[5] Gaberscek M,K zmaa M,Jamnika J. Electrochemical Kinetics of Porous, Carbon-decorated LiFePO4 Cathodes: Separation of Wiring Effects from Solid State Diffusion[J]. Phys Chem Chem Phys,2007,9:1815-1820.

[6] Mba J M A,Masquelier C,Suard E. Synthesis and Crystallographic Study of Homeotypic LiVPO4F and LiVPO4O[J]. Chem Mater,2012,24(6):1223-1234.

[7] Li Y Z,Zhou Z,Gao X P,et al. A Novel Sol-gel Method to Synthesize Nanocrystalline LiVPO4F and Its Electrochemical Li Intercalation Performances[J]. J Power Sources,2006,160(1):633-637.

[8] Zhou F,Zhao X M,Dahn J R. Reactivity of Charged LiVPO4F with 1 M LiPF6 EC:DEC Electrolyte at High Temperature as Studied by Accelerating Rate Calorimetry[J]. Electrochem Commun,2009,11(3):589-591.

[9] Pan A Q,Liu J,Zhang J G,et al. Nano-structured Li3V2(PO4)3/Carbon Composite for High-rate Lithium-ion Batteries[J]. Electrochem Commun,2010,12:1674-1677.

[10] Zhu J F,Yang R S,Wu K L. Synthesis of Li3V2(PO4)3/Reduced Ggraphene Oxide Cathode Material with High-rate Capability[J]. Ionics,2013,19:577 580.

[11] Tang A P,Wang X Y,Liu Z M. Electrochemical Behavior of Li3V2(PO4)3/C Composite Cathode Material for Lithiumion Batteries[J]. Mater Lett,2008,62(10/11):1646-1648.

[12] Azmi B M,Ishihara T,Nishiguchi H,et al. Vanadyl Phosphates of VOPO4 as a Cathode of Li Ion Rechargeable Batteries[J]. J Power Sources,2003,119-122:273-277.

[13] Azmi B M,Ishihara T,Nishiguchi H,et al. Cathodic Performance of VOPO4 with Various Crystal Phases for Li Ion Rechargeable Battery[J]. Electrochim Acta,2002,48(2):165-170.

[14] Ganbicher J,Mercier T L,Chahre Y,et al. Li/β-VOPO4:A New 4V System for Lithium Batteries[J]. J Electrochem Soc,1999,146(12):4375-4379.

[15] Hameed A S,Nagarathinam M,Reddy M V,et al. Synthesis and Electrochemical Studies of Layer-structured Metastable αⅠ-LiVOPO4[J]. J Mater Chem,2012,22:7206-7213.

[16] Saravanan K,Lee H S,Kuezma M,et al. Hollow α-LiVOPO4 Sphere Cathodes for High Energy Li-ion Battery Application[J]. J Mater Chem,2011,21:10042-10050.

[17] Kerr T A,Gaubicher J,Nazar L F. Highly Reversible Li Insertion at 4 V in ε-VOPO4/α-LiVOPO4 Cathodes[J]. Electrochem Solid-State Lett,2000,3(10):460-462.

[18] HE Zeqiang,LIANG Kai,XIONG Lizhi. Effect of AlPO4 Coating on the Electrochemical Properties of LiVOPO4 Cathode Material[J]. Mater Rev B,2011,25(4):61-64(in Chinese).

何则强,梁凯,熊利芝. AlPO4包覆对LiVOPO4电化学性能的影响[J]. 材料导报B,2011,25(4):61-64.

[19] Song Y,Zavalij P Z,Whittingham M S. ε-VOPO4:Electrochemical Synthesis and Enhanced Cathode Behavior[J]. J Electrochem Soc,2005,152(4):721-728.

[20] Lii K H,Li C H,Cheng Y. Hydrothermal Synthesis, Structure, and Magnetic Properties of a New Polymorph of Lithium Vanadyl(Ⅳ) Orthophosphate:β-LiVOPO4[J]. J Solid State Chem,1991,95(2):352-359.

[21] Barker J,Saidi M Y,Swoye J L. Electrochemical Properties of Beta-LiVOPO4 Prepared by Carbothermal Reduction[J]. J Electrochem Soc,2004,151(6):796-800.

[22] Launay M,Boucher F,Gressier P,et al. A DFT Study of Lithium Battery Materials:Application to the β-VOXO4 Systems(X=P,As,S)[J]. J Solid State Chem,2003,176:556-566.

[23] Dupré N,Wallez G,Gaubicher J,et al. Phase Transition Induced by Lithium Insertion in αⅠ- and αⅡ-VOPO4[J]. J Solid State Chem,2004,177:2896-2902.

[24] Allen C J,Jia Q Y,Chinnasamy C N. Synthesis, Structure and Electrochemistry of Lithium Vanadium Phosphate Cathode Materials[J]. J Electrochem Soc,2011,158(12):1250-1259.

[25] Paul B J,Mathew V,Do G X,et al. Enhanced Storage Capacities in Carbon-coated Triclinic-LiVOPO4 Cathode with Porous Structure for Li-Ion Batteries[J]. Electrochem Lett,2012,1(4):63-65.

[26] Nagamine K,Honma T,Komatsu T. Selective Synthesis of Lithium Ion-conductive β-LiVOPO4 Crystals via Glass-ceramic Processing[J]. J Am Ceram Soc,2008,91(12):3920-3925.

[27] Nagamine K,Honma T，Komatsu T. Fabrication of LiVOPO4/Carbon Composite via Glass-ceramic Processing[J]. Mater Sci Eng,2011,21:1-5.

[28] Tang A P,He Z Q,Shen J,et al. Synthesis and Characterization of LiVOPO4 Cathode Material by Solid State Method[J]. Adv Mater Res,2012,554-556:436-439.

[29] Dupré N,Gaubicher J,Angenault J,et al. Electrochemical Performance of Different Li-VOPO4 Systems[J]. J Power Sources,2001,97/98:532-534.

[30] Ren M M,Zhou Z,Gao X P,et al. LiVOPO4 Hollow Microspheres:One-pot Hydrothermal Synthesis with Reactants as Self-sacrifice Templates and Lithium Intercalation Performances[J]. J Phys Chem C,2008,112:13043-13046.

[31] Tang A P,Shen J,Hu Y J,et al. Electrochemical Performance of α-LiVOPO4/Carbon Composite Material Synthesized by Sol-gel Method[J]. J Electrochem Soc,2013,161(1):10-13.

[32] Calero D L,Bruque S,Miuela.G,et al. Topotactic Litium Exchange in the Precursor Catalyst VOHPO4·0.5H2O:The Crystal Structure of LiVOPO4·0.5H2O[J]. J Solid State Chem,1993,103:481-489.

[33] Azmi B M,Ishihara T,Nishiguchi H,et al. LiVOPO4 as a New Cathode Materials for Li-ion Rechargeable Battery[J]. J Power Sources,2005,146:525-528.

[34] Azmi B M,Ishihara T,Nishiguchi H,et al. Optimized LiVOPO4 for Cathodes in Li-ion Rechargeable Batteries[J]. Ionics,2005,11(5/6):402-405.

[35] Xiong L Zi,He Z Q. A New Rheological Phase Route to Synthesize Nano-LiVOPO4 Cathode Material for Lithium Ion Batteries[J]. Acta Phys-Chim Sin,2010,26(3):573-577.

[36] Park J S,Myung S T. LiVOPO4 as a Negative Electrode Material for Rrechargeable Lithium Batteries[C]//The 224th ECS Meeting. San Francisco,2013:Abstract#890.

[37] Dompablo M E A,Rozier P,Morcrette M,et al. Electrochemical Data Transferability within LiyVOXO4(X=Si,Ge0.5Si0.5,Ge,Si0.5As0.5,Si0.5P0.5,As,P) Polyoxyanionic Compounds[J]. Chem Mater,2007,19:2411-2422.

[38] Ren M M,Zhou Z,Su L W. LiVOPO4:A Cathode Material for 4 V Lithium Ion Batteries[J]. J Power Sources,2008,189(1):786-789.

[39] Azmi M B,Man Z,Maitra S. Electrochemical Performance of Cathode LiVOPO4 Doped with Mo and W[J]. Trans Indian Ceram Soc,2013,72(2):108-112.

[40] XIONG Lizhi,LIU Wenping,JIANG Jianbo,et al. Preparation and Electrochemieal Properties of LiMnxV1-xOPO4 [C]//The 16th National Conference of Solid Solid Ionics & International Forum on Next Generation Energy Material and Technology,Chengdu,2012:29(in Chinese).

熊利芝,刘文萍,蒋剑波,等. LiMn1-xVxOPO4的制备与电化学性能[C]//第十六届全国固态离子学学术会议暨下一代能源材料与技术国际研讨会—会议论文摘要集,成都,2012:29.