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

参考文献

[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 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 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

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 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 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

[1]	张桥, 谭薇, 宁勇祺, 聂国政, 蔡孟秋, 王俊年, 朱慧平, 赵宇清. 基于机器学习和第一性原理计算的Janus材料的预测. , 2024, 73(23): 230201. doi: 10.7498/aps.73.20241278
[2]	杨海林, 陈琦丽, 顾星, 林宁. 氧原子在氟化石墨烯上扩散的第一性原理计算. , 2023, 72(1): 016801. doi: 10.7498/aps.72.20221630
[3]	余跃, 杨恒玉, 周五星, 欧阳滔, 谢国锋. 第一性原理研究单层Ge₂X₄S₂(X = P, As)的热电性能. , 2023, 72(7): 077201. doi: 10.7498/aps.72.20222244
[4]	钟淑琳, 仇家豪, 罗文崴, 吴木生. 稀土掺杂对LiFePO₄性能影响的第一性原理研究. , 2021, 70(15): 158203. doi: 10.7498/aps.70.20210227
[5]	尹媛, 李玲, 尹万健. 太阳能电池材料缺陷的理论与计算研究. , 2020, 69(17): 177101. doi: 10.7498/aps.69.20200656
[6]	王艳, 曹仟慧, 胡翠娥, 曾召益. Ce-La-Th合金高压相变的第一性原理计算. , 2019, 68(8): 086401. doi: 10.7498/aps.68.20182128
[7]	胡前库, 侯一鸣, 吴庆华, 秦双红, 王李波, 周爱国. 过渡金属硼碳化物TM₃B₃C和TM₄B₃C₂稳定性和性能的理论计算. , 2019, 68(9): 096201. doi: 10.7498/aps.68.20190158
[8]	闫小童, 侯育花, 郑寿红, 黄有林, 陶小马. Ga, Ge, As掺杂对锂离子电池正极材料Li₂CoSiO₄的电化学特性和电子结构影响的第一性原理研究. , 2019, 68(18): 187101. doi: 10.7498/aps.68.20190503
[9]	白静, 王晓书, 俎启睿, 赵骧, 左良. Ni-X-In(X=Mn,Fe和Co)合金的缺陷稳定性和磁性能的第一性原理研究. , 2016, 65(9): 096103. doi: 10.7498/aps.65.096103
[10]	袁振坤, 许鹏, 陈时友. 多元半导体光伏材料中晶格缺陷的计算预测. , 2015, 64(18): 186102. doi: 10.7498/aps.64.186102
[11]	张召富, 周铁戈, 左旭. 氧、硫掺杂六方氮化硼单层的第一性原理计算. , 2013, 62(8): 083102. doi: 10.7498/aps.62.083102
[12]	焦照勇, 郭永亮, 牛毅君, 张现周. 缺陷黄铜矿结构Xga2S4 (X=Zn, Cd, Hg)晶体电子结构和光学性质的第一性原理研究. , 2013, 62(7): 073101. doi: 10.7498/aps.62.073101
[13]	窦俊青, 康雪雅, 吐尔迪·吾买尔, 华宁, 韩英. Mn掺杂LiFePO4的第一性原理研究. , 2012, 61(8): 087101. doi: 10.7498/aps.61.087101
[14]	汝强, 胡社军, 赵灵智. LixFePO4(x=0.0, 0.75, 1.0)电子结构与弹性性质的第一性原理研究. , 2011, 60(3): 036301. doi: 10.7498/aps.60.036301
[15]	忻晓桂, 陈香, 周晶晶, 施思齐. LiFePO4 晶格动力学性质的第一性原理研究. , 2011, 60(2): 028201. doi: 10.7498/aps.60.028201
[16]	谭兴毅, 金克新, 陈长乐, 周超超. YFe2B2电子结构的第一性原理计算. , 2010, 59(5): 3414-3417. doi: 10.7498/aps.59.3414
[17]	顾牡, 林玲, 刘波, 刘小林, 黄世明, 倪晨. M’型GdTaO4电子结构的第一性原理研究. , 2010, 59(4): 2836-2842. doi: 10.7498/aps.59.2836
[18]	胡方, 明星, 范厚刚, 陈岗, 王春忠, 魏英进, 黄祖飞. 梯形化合物NaV2O4F电子结构的第一性原理研究. , 2009, 58(2): 1173-1178. doi: 10.7498/aps.58.1173
[19]	刘利花, 张颖, 吕广宏, 邓胜华, 王天民. Sr偏析Al晶界结构的第一性原理计算. , 2008, 57(7): 4428-4433. doi: 10.7498/aps.57.4428
[20]	宋庆功, 王延峰, 宋庆龙, 康建海, 褚勇. 插层化合物Ag1/4TiSe2电子结构的第一性原理研究. , 2008, 57(12): 7827-7832. doi: 10.7498/aps.57.7827

计量

文章访问数: 8169
PDF下载量: 827
被引次数: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

搜索

留言板