LiFePO4中对位缺陷的第一性原理研究

张华; 唐元昊; 周薇薇; 李沛娟; 施思齐

doi:10.7498/aps.59.5135

摘要

基于考虑了Fe-3d电子间的库仑作用U和交换作用J的GGA+U方案,应用第一性原理计算方法系统研究了LiFePO4的对位缺陷,以及对位缺陷的形成对材料的电导率和离子扩散速率的影响.结果表明,Li/Fe交换缺陷是最容易形成的,形成缺陷后的Fe—O键变长,扩宽了Li离子传输通道,有利于Li离子在通道中的扩散,对材料电化学性能的改善起到了一定的作用.

关键词:

The antisite defect, electronic conductivity and ionic dynamic properties of LiFePO4 have been investigated using first-principles density functional theory taking into account the on-site Coulomb interaction within the GGA+U scheme. Results indicate the Li/Fe exchange defect is the most preferred to occur in LiFePO4, which causes the Fe—O bond length to change in the direction favoring the formation of Li+ diffusion channels, hence improving the ionic dynamic properties of the olivine LiFePO4.

Keywords:

作者及机构信息

1.
浙江理工大学物理系,光电材料与器件中心,杭州 310018

基金项目: 国家自然科学基金(批准号:50802089)、浙江省"钱江人才计划"(批准号: 2007R10028)、教育部留学回国人员科研启动基金(批准号:[2008] 890)、浙江省自然科学基金(批准号:Y4090280)和江西省自然科学基金(批准号:2008GZW0014)资助的课题.

Authors and contacts

1.
Department of Physics, Center for Optoelectronics Materials and Devices, Zhejiang Sci-Tech University, Hangzhou 310018, China

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施引文献

[1]	Hou Z F, Liu H Y, Zhu Z Z, Huang M C, Yang Y 2003 Acta Phys. Sin. 52 952 (in Chinese) [侯柱峰、刘慧英、朱梓忠、黄美纯、杨勇 2003 物理学报 52 952]
[2]	Amin R, Lin C, Maier J 2008 Phys. Chem. Chem. Phys. 10 3524
[3]	2006 J. Power Sources 159 282
[4]	Huang H, Yin S C, Nazar L F 2001 Electrochem.Solid-State Lett. 4 A170
[5]	Islam M S, Driscoll D J, Fisher C A J, Slater P R 2005 Chem. Mater. 17 5085
[6]	Sigle W, Amin R, Weichert K, Aken P A, Maier J 2009 Electrochem.Solid-State Lett. 128 A151
[7]	Padhi A K, Nanjundaswamy K S, Masquelier C, Okada S, Goodenough J B 1997 J. Electrochem. Soc. 144 1188
[8]	Ravet N, Chouinard Y, Magnan J F, Besner S, Gacuthier M, Armand M 2001 J. Power Sources 503 97
[9]	Dominko D, Gaberscek M, Drofenik J, Bele M, Jamnik J 2003 Electron. Acta 48 3709
[10]	Choi D, Kumta P 2007 J. Power Sources 163 1064
[11]	Chung S Y, Bloking J T, Chiang Y M 2002 Nat. Mater. 1 123
[12]	Chung S Y, Chiang Y M 2003 Electrochem. Solid-State Lett. 6 A278
[13]	Herle P S, Ellis B, Coombs N, Nazar L F 2004 Nat. Mater. 3 147
[14]	Barker J, Saidi M Y, Swoyer J L 2003 Electrochem.Solid-State Lett. 6 A53
[15]	Islam M S, Driscoll D J, J Fisher C A, Slater P R 2005 Chem. Mater. 17 5085
[16]	Shi S Q, Ouyang C Y, Wang D S, Wang Z X, Chen L Q 2003 Phys. Rev. B 68 19508
[17]	Hong J, Wang C, Kasavajjula U 2006 J. Power Sources 162 1289
[18]	Mi C H, Zhang X G, Zhao X B, Li H L 2006 Mater. Sci. Eng. B 8 129
[19]	Wang D Y, Li H, Shi S Q, Huang X J, Chen L Q 2005 Electron. Acta 50 2955
[20]	Wang G X, Needham S, Yao J, Wang J Z, Liu R S, Liu H K
[21]	Ouyang X F, Shi S Q, Ouyang C Y, Jiang D Y, Liu D S, Ye Z Q, Lei M S 2007 Chin. Phys. Soc. 10 3042
[22]	Shi S Q, Ouyang C Y, Xiong Z H, Liu L J, Wang Z X, Li H, Wang D S, Chen L Q, Huang X J 2005 Phys. Rev. B 71 144404
[23]	Luo Z, Di N L, Kou Z Q, Cheng Z H, Liu L J, Chen L Q, Huang X J 2004 Chin. Phys. 13 2158
[24]	Shi S Q, Zhang H, Ke X Z, Ouyang C Y, Lei M S, Chen L Q 2009 Phys. Lett. A 44 4906
[25]	Ouyang X F, Lei M L, Shi S Q, Luo C L, Liu D S, Jiang D Y, Ye Z Q, Lei M S 2009 J. Alloys Compd. 476 462
[26]	Liu H, Xie J Y 2009 J. Mater. Process. Technol. 209 477
[27]	Blchl P E 1994 Phys. Rev. B 50 17953
[28]	Kresse G, Furthmüller J 1996 Phys. Rev. B 54 11169
[29]	Perdew J P, Chevary J A, Vosko S H, Jackson K A, Pederson M R, Singh D J, Fiolhais C 1992 Phys. Rev. B 46 6671
[30]	Liechtenstein A I, Anisimov V I, Zaanen J 1995 Phys. Rev. B 52 R5467
[31]	Zhou F, Kang K, Maxisch T, Ceder G, Morgan D 2004 Solid State Commun. 132 181
[32]	Cococcioni M, de Gironcoli S 2005 Phys. Rev. B 71 035105
[33]	Methfessel M, Paxton A T 1989 Phys. Rev. B 40 3616
[34]	Huang Y X, Cao Q X, Li Z M, Li G F, Wang Y P, Wei Y G 2009 Acta Phys. Sin. 58 8002 (in Chinese) [黄云霞、曹全喜、李智敏、李桂芳、王毓鹏、卫云鸽 2009 物理学报 58 8002]
[35]	Fisher C A J, Hart Prieto V M, Saiful Islam M 2008 Chem. Mater. 20 5907
[36]	Islam M S 2005 Chem. Mater. 17 5085
[37]	Ouyang C Y, Shi S Q, Wang Z X, Huang X J, Chen L Q 2004 Phys. Rev. B 69 104303
[38]	Ouyang C Y, Shi S Q, Wang Z X, Li H, Huang X J, Chen L Q 2004 J. Phys. : Condens. Matter 16 2265
[39]	Morgan D, van der Ven A, Ceder G 2004 Electrochem. Solid-State Lett. 7 A30

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