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

汝强; 胡社军; 赵灵智

doi:10.7498/aps.60.036301

摘要

采用基于密度泛函理论的第一性原理研究方法,计算了不同嵌锂态LixFePO4(x=0,0.75,1.0)的电子结构. 对于橄榄石型LixFePO4正极材料,虽然Fe3d电子在费米能级附近相互交错,但由于受晶体场作用的限制,并不能真正成为自由电子,Fe3d电子对体系的导电性没有很大贡献,而Fe—O键在低能成键区形成p-d杂化的局域态共价键对稳定合金骨架具有重要作用. 随着锂离子的脱

关键词:

Based on density functional theory of the first-principle, the electronic structures of LiFexPO4 (x=0.0, 0.75, 1.0) are calculated. The calculated results show that Fe3d states restrained by crystalline field cannot contribute to free electrons even though Fe3d states cross the Fermi level. Meanwhile, Fe—O bond is beneficial to stabilize the alloy structure due to the p-d hybrid orbital. With lithium ion extraction, the enhanced covalent bonds appear. In LixFePO4 system, the strength of covalent bond is in the order of P—O>Fe—O>Li—O. LixFePO4 system displays brittleness of material characteristic, and the LixFePO4(x=1.0, 0.75) with lithium intercalation have stronger average bonding strength than that of FePO4.

Keywords:

作者及机构信息

1.
广东省高等学校量子信息技术重点实验室,华南师范大学物理与电信工程学院,广州 510006

基金项目: 国家自然科学基金(批准号: 50771046),广东高校优秀青年创新人才培育项目育苗工程(批准号:C10179)和广东省自然科学基金(批准号: 9451063101002082)资助的课题.

Authors and contacts

1.
Laboratory of Quantum Information Technology, School of Physics & Telecommunication Engineering, South China Normal University, Guangzhou 510006,China

参考文献

[1]	Chihiro Yada, Yasutoshi Iriyama, Soon-Ki Jeong 2005 J. Power Sources 146 559
[2]	Tarascon J M, Armand M 2001 Nature 414 360
[3]	State Ionics 130 41
[4]	Ouyang C Y, Shi S Q, Wang Z X, Huang X J, Chen L Q 2004 Phys. Rev. B 69 104303
[5]	Shi S Q, Zhang H, Ke X Z, Ouyang C Y, Lei M S, Chen L Q 2009 Phys. Lett. A 373 4096
[6]	Ouyang C Y, Shi S Q, Fang Q, Lei M S 2008 J. Power Sources 175 891
[7]	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
[8]	Huang H, Yin S C, Nazar L F 2001 Electrochem. Solid-State Lett. 4 A170
[9]	Ravet N, Chouinard Y, Armand M 2001 J. Power Sources 503 97
[10]	Ouyang C Y, Wang D Y, Shi S Q, Wang Z X, Li H, Huang X J, Chen L Q 2006 Chin. Phys. Lett. 23 61
[11]	Shi S Q, Liu L J, Ouyang C Y, Wang D S, Wang Z X, Chen L Q, Huang X J 2003 Phys. Rev. B 68 195108
[12]	Ouyang C Y, Shi S Q, Wang Z X, Li H, Huang X J, Chen L Q 2004 J. Phys.: Condens. Matter 16 2265
[13]	Wang D Y, Li H, Shi S Q, Huang X J, Chen L Q 2005 Electrochim. Acta 50 2955
[14]	Ceder G, Chiang Y M, Sadoway D R, Aydinol M K, Jang Y I, Huang B 1998 Nature 392 694
[15]	Shi S Q, Ouyang C Y, Lei M S, Tang W H 2007 J. Power Sources 171 908
[16]	Hu L Y, Xiong Z H, Ouyang C Y, Shi S Q, Ji Y H, Lei M S, Wang Z X, Li H, Huang X J, Chen L Q 2005 Phys. Rev. B 71 125433
[17]	Ouyang C Y, Du Y L, Shi S Q, Lei M S 2009 Phys. Lett. A 373 2796
[18]	Shi S Q, Wang D S, Meng S, Chen L Q, Huang X J 2003 Phys. Rev. B 67 115130
[19]	Shi S Q, Ouyang C Y, Wang D S, Chen L Q, Huang X J 2003 Solid State Commun. 126 531
[20]	Ouyang C Y, Shi S Q, Wang Z X, Huang X J, Chen L Q 2004 Solid State Commun. 130 501
[21]	Ouyang C Y, Du Y L, Shi S Q, Lei M S 2009 Phys. Lett. A 373 2796
[22]	Andersson A S, Kalska B, Hggstrm L, Thomas J O 2000 Solid
[23]	Piana M, Arrabito M, Bodoardo S, D'Epifanio A, Satolli D, Croce F, Scrosati B 2002 Ionics 8 17
[24]	Wang L L, Ma P H, Li F Q, Zhu G Q 2008 Chemistry 1 17 (in Chinese) [王连亮、马培华、李法强、诸葛芹 2008 化学通报 1 17]
[25]	Segall M D, Philip J D Lindan, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 Journal of Physics 14 2717
[26]	Hou X H, Hu S J, Li W S, Ru Q, Yu H W, Huang Z W 2008 Chin. Phys. B 17 3422
[27]	Hou X H, Hu S J, Li W S, Zhao L Z, Yu H W, Tan C L 2008 Acta Phys. Sin. 57 2374(in Chinese)[侯贤华、胡社军、李伟善、赵灵智、余洪文、谭春林 2008 物理学报 57 2374]
[28]	Ormeci A, Chu F, Wills J M, Mitchell T E, Albers R C, Thoma D J, Chen S P 1996 Phys. Rev. B 54 12753
[29]	Padhi A K, Nanjundaswamy K S, Goodenough J B 1997 J. Electrochem. Soc. 144 1188
[30]	Fu C L, Wang X D, Ye Y, HO K M 1999 Intermetallics 7 179
[31]	Yu C, Liu J Y, Lu H, Li P L, Chen J M 2007 Intermetallics 15 1471
[32]	Andersson A S, Thomos J O 2001 J. Power Sources 97-98 498
[33]	Anderson O L 1963 J. Phys. Chem. Solids 24 909
[34]	Thomas Maxisch, Gerband Ceder 2006 Phys. Rev. B 73 174112
[35]	Pugh S F 1954 Philos. Mag. 45 823
[36]	Wang D, Wu X, Wang Z, Chen L 2005 J. Power Sources 140 125

施引文献

[1]	Chihiro Yada, Yasutoshi Iriyama, Soon-Ki Jeong 2005 J. Power Sources 146 559
[2]	Tarascon J M, Armand M 2001 Nature 414 360
[3]	State Ionics 130 41
[4]	Ouyang C Y, Shi S Q, Wang Z X, Huang X J, Chen L Q 2004 Phys. Rev. B 69 104303
[5]	Shi S Q, Zhang H, Ke X Z, Ouyang C Y, Lei M S, Chen L Q 2009 Phys. Lett. A 373 4096
[6]	Ouyang C Y, Shi S Q, Fang Q, Lei M S 2008 J. Power Sources 175 891
[7]	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
[8]	Huang H, Yin S C, Nazar L F 2001 Electrochem. Solid-State Lett. 4 A170
[9]	Ravet N, Chouinard Y, Armand M 2001 J. Power Sources 503 97
[10]	Ouyang C Y, Wang D Y, Shi S Q, Wang Z X, Li H, Huang X J, Chen L Q 2006 Chin. Phys. Lett. 23 61
[11]	Shi S Q, Liu L J, Ouyang C Y, Wang D S, Wang Z X, Chen L Q, Huang X J 2003 Phys. Rev. B 68 195108
[12]	Ouyang C Y, Shi S Q, Wang Z X, Li H, Huang X J, Chen L Q 2004 J. Phys.: Condens. Matter 16 2265
[13]	Wang D Y, Li H, Shi S Q, Huang X J, Chen L Q 2005 Electrochim. Acta 50 2955
[14]	Ceder G, Chiang Y M, Sadoway D R, Aydinol M K, Jang Y I, Huang B 1998 Nature 392 694
[15]	Shi S Q, Ouyang C Y, Lei M S, Tang W H 2007 J. Power Sources 171 908
[16]	Hu L Y, Xiong Z H, Ouyang C Y, Shi S Q, Ji Y H, Lei M S, Wang Z X, Li H, Huang X J, Chen L Q 2005 Phys. Rev. B 71 125433
[17]	Ouyang C Y, Du Y L, Shi S Q, Lei M S 2009 Phys. Lett. A 373 2796
[18]	Shi S Q, Wang D S, Meng S, Chen L Q, Huang X J 2003 Phys. Rev. B 67 115130
[19]	Shi S Q, Ouyang C Y, Wang D S, Chen L Q, Huang X J 2003 Solid State Commun. 126 531
[20]	Ouyang C Y, Shi S Q, Wang Z X, Huang X J, Chen L Q 2004 Solid State Commun. 130 501
[21]	Ouyang C Y, Du Y L, Shi S Q, Lei M S 2009 Phys. Lett. A 373 2796
[22]	Andersson A S, Kalska B, Hggstrm L, Thomas J O 2000 Solid
[23]	Piana M, Arrabito M, Bodoardo S, D'Epifanio A, Satolli D, Croce F, Scrosati B 2002 Ionics 8 17
[24]	Wang L L, Ma P H, Li F Q, Zhu G Q 2008 Chemistry 1 17 (in Chinese) [王连亮、马培华、李法强、诸葛芹 2008 化学通报 1 17]
[25]	Segall M D, Philip J D Lindan, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 Journal of Physics 14 2717
[26]	Hou X H, Hu S J, Li W S, Ru Q, Yu H W, Huang Z W 2008 Chin. Phys. B 17 3422
[27]	Hou X H, Hu S J, Li W S, Zhao L Z, Yu H W, Tan C L 2008 Acta Phys. Sin. 57 2374(in Chinese)[侯贤华、胡社军、李伟善、赵灵智、余洪文、谭春林 2008 物理学报 57 2374]
[28]	Ormeci A, Chu F, Wills J M, Mitchell T E, Albers R C, Thoma D J, Chen S P 1996 Phys. Rev. B 54 12753
[29]	Padhi A K, Nanjundaswamy K S, Goodenough J B 1997 J. Electrochem. Soc. 144 1188
[30]	Fu C L, Wang X D, Ye Y, HO K M 1999 Intermetallics 7 179
[31]	Yu C, Liu J Y, Lu H, Li P L, Chen J M 2007 Intermetallics 15 1471
[32]	Andersson A S, Thomos J O 2001 J. Power Sources 97-98 498
[33]	Anderson O L 1963 J. Phys. Chem. Solids 24 909
[34]	Thomas Maxisch, Gerband Ceder 2006 Phys. Rev. B 73 174112
[35]	Pugh S F 1954 Philos. Mag. 45 823
[36]	Wang D, Wu X, Wang Z, Chen L 2005 J. Power Sources 140 125

计量

文章访问数: 8159
PDF下载量: 797
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