应变对层状锰系锂离子电池正极材料输出电压的影响

任晓栋; 刘建军; 张文清

doi:10.7498/aps.61.183101

摘要

利用第一性原理方法系统研究了不同应变模式对LiMnO2和Li2MnO3输出电压的影响, 建立了输出电压与弹性常数及应变之间的关系. 发现所有应变对输出电压都是降低的, 且应变效应是各向异性的. 大部分的单轴应变5%时对输出电压的降低都小于0.1 V. 由于层状的电极材料层间的键合作用较弱, 且受脱锂后形成的锂空位影响较大, 当从锂层脱出锂时, 垂直于层方向的应变对输出电压影响较大; 而对Li2MnO3系统从过渡金属层中脱锂时, 平行于层的应变对输出电压影响更大. Li2MnO3骨架支撑的层状固溶体系中, 应变使高电压充电阶段的电压维持在截断电压之下, 并打开过渡金属层中锂的迁移通道, 产生较为持久的充电而可能获得较大的充电容量.

关键词:

输出电压 /
应变 /
弹性常数 /
Li2MnO3

Abstract

The strain effects on the intercalation potentials of LiMnO2 and Li2MnO3 are investigated by the first principles method, and the relationship between the intercalation potential and the strain is given in the form of elastic response. All the modes of strain reduce the intercalation potential and the effect is anisotropic. Most of the single modes reduce the potential by less than 0.1 V when the strains are 5%. The bonding between the host layers is rather sensitive to the strain perpendicular to the host layer when the lithium vacancy left by lithium extraction is in the lithium layer, thus that strain brings more reduction to the intercalation potential; whereas for the Li2MnO3 system when lithium is extracted form the transition metal layer, the strain along the host layer brings more reduction to the potential. For the Li2MnO3-stabilized LiMO2 (M=Mn, Ni, Co) solid solution system, the strain can keep the voltage of the high potential charging stage lower than the cut-off voltage, and open up the migrating pathway of lithium in the transition metal layer, therefore the charging can last a long time and larger charging capacity is achieved.

Keywords:

作者及机构信息

1.
中国科学院上海硅酸盐研究所, 高性能陶瓷与超微结构国家重点实验室, 上海 200050

基金项目: 国家自然科学基金(批准号: 50825205)资助的课题.

Authors and contacts

1.
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 50825205).

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施引文献

[1]	Ellis B L, Lee K T, Nazar L F 2010 Chem. Mater. 22 691
[2]	Goodenough J B, Kim Y 2010 Chem. Mater. 22 587
[3]	Tarascon J M, Armand M 2001 Nature 414 359
[4]	Johnson C S, Li N C, Lefief C, Thackeray M M 2007 Electrochem. Commun. 9 787
[5]	Thackeray M M, Kang S H, Johnson C S, Vaughey J T, Benedek R, Hackney S A 2007 J. Mater. Chem. 17 3112
[6]	Thackeray M M, Johnson C S, Vaughey J T, Li N, Hackney S A 2005 J. Mater. Chem. 15 2257
[7]	Striebel K A, Sierra A, Shim J, Wang C W, Sastry A M 2004 J. Power Sources 134 241
[8]	Gnanaraj J S, Cohen Y S, Levi M D, Aurbach D 2001 J. Electroanal. Chem. 516 89
[9]	Meethong N, Huang H S, Speakman S A, Carter W C, Chiang Y M 2007 Adv. Funct. Mater. 17 1115
[10]	Chung K Y, Kim K B 2004 Electrochim. Acta 49 3327
[11]	Koyama Y, Chin T E, Rhyner U, Holman R K, Hall S R, Chiang Y M 2006 Adv. Funct. Mater. 16 492
[12]	Aydinol M K, Kohan A F, Ceder G, Cho K, Joannopoulos J 1997 Phys. Rev. B 56 1354
[13]	Zhou F, Cococcioni M, Marianetti C A, Morgan D, Ceder G 2004 Phys. Rev. B 70 2351211
[14]	Chevrier V L, Ong S P, Armiento R, Chan M K Y, Ceder G 2010 Phys. Rev. B 82 0751221
[15]	Fast L, Wills J M, Johansson B, Eriksson O 1995 Phys. Rev. B 51 17431
[16]	Ru Q, Hu S J, Zhao L Z 2011 Acta Phys. Sin. 60 036301 (in Chinese) [汝强, 胡社军, 赵灵智 2011 物理学报 60 036301]
[17]	Wang Y J 1966 Acta Phys. Sin. 22 214 (in Chinese) [汪永江 1966 物理学报 22 214]
[18]	Hohenberg P, Kohn W 1964 Phys. Rev. 136 B864
[19]	Kohn W, Sham L J 1965 Phys. Rev. 140 A 1133
[20]	Kresse G, Furthmüller J 1996 Phys. Rev. B 54 11169
[21]	Blöchl P E 1994 Phys. Rev. B 50 17953
[22]	Hua X, Chen X, Goddard W A 1997 Phys. Rev. B 55 16103
[23]	Perdew J P, Burke K, Ernzerhof M 1997 Phys. Rev. Lett. 78 1396
[24]	Anisimov V I, Zaanen J, Andersen O K 1991 Phys. Rev. B 44 943
[25]	Cococcioni M, de Gironcoli S 2005 Phys. Rev. B 71 0351051
[26]	Koyama Y, Tanaka I, Nagao M, Kanno R 2009 J. Power Sources 189 798
[27]	Armstrong A R, Bruce P G 1996 Nature 381 499
[28]	Boulineau A, Croguennec L, Delmas C, Weill F 2010 Solid State Ionics 180 1652
[29]	Felice R A, Trivisonno J, Schuele D E 1977 Phys. Rev. B 16 5173
[30]	Pacalo R E, Graham E K 1991 Phys. Chem. Miner. 18 69
[31]	Piszora P 2007 Z. Kristallogr. 387
[32]	Zhang Y, Lv G H, Dong S H, Wang T M 2006 Acta Phys. Sin. 55 2901 (in Chinese) [张颖, 吕广宏, 邓胜华, 王天民 2006 物理学报 55 2901]
[33]	Wu Y, Manthiram A 2009 Solid State Ionics 180 50
[34]	Liu J, Reeja-Jayan B, Manthiram A 2010 J. Phys. Chem. C 114 9528
[35]	Johnson C S, Li N C, Lefief C, Vaughey J T, Thackeray M M 2008 Chem. Mater. 20 6095
[36]	Meng Y S, Arroyo-de Dompablo M E 2009 Energ. Environ. Sci. 2 589

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