Structural and magnetic properties of LiNi0.5Mn1.5O4 and LiNi0.5Mn1.5O4-δ spinels: A first-principles study

doi:10.1088/1674-1056/21/12/128202

Abstract Structural and magnetic properties of LiNi_0.5Mn_1.5O₄ and LiNi_0.5Mn_1.5O_4-δ are investigated using density-functional theory calculations. Results indicate that nonstoichiometric LiNi_0.5Mn_1.5O_4-δ and stoichiometric LiNi_0.5Mn_1.5O₄ exhibit two different structures, i.e., the face-centred cubic (Fd-3m) and primitive, or simple, cubic (P4₃32) space groups, respectively. It is found that the magnetic ground state of LiNi_0.5Mn_1.5O₄ (P4₃32 and Fd-3m) is ferrimagnetic state in which the Ni and Mn sublattices are ferromagnetically ordered along the [110] direction whereas they are antiferromagnetic with respect to each other. We demonstrate that it is the presence of O-vacancy in LiNi_0.5Mn_1.5O_4-δ with the Fd-3m space group that results in its superior electronic conductivity compared with LiNi_0.5Mn_1.5O₄ with the P4₃32 space group.

Keywords: LiNi_0.5Mn_1.5O₄ magnetic properties crystal structures first-principles calculations

Received: 21 May 2012
Revised: 19 June 2012
Accepted manuscript online:

PACS:	82.47.Aa	(Lithium-ion batteries)
	31.15.A-	(Ab initio calculations)
	71.20.-b	(Electron density of states and band structure of crystalline solids)

Fund: Project supported by the National Natural Science Foundation of China (Grant Nos. 51072183 and 50802089) and the Natural Science Foundation of Zhejiang Province, China (Grant No. Y4090280).

Corresponding Authors: Shi Si-Qi
E-mail: siqishihz@gmail.com

Cite this article:

Xin Xiao-Gui (忻晓桂), Shen Jing-Qin (沈静琴), Shi Si-Qi (施思齐) Structural and magnetic properties of LiNi_0.5Mn_1.5O₄ and LiNi_0.5Mn_1.5O_4-δ spinels: A first-principles study 2012 Chin. Phys. B 21 128202

[1]	Wu X L, Jiang L Y, Cao F F, Guo Y G and Wan L J 2009 Adv. Mater. 21 2710
[2]	Shi S L, Liu Y G, Zhang J Y and Wang T H 2009 Chin. Phys. B 18 4564
[3]	Hou X H, Hu S J, Li W S, Ru Q, Yu H W and Huang Z W 2008 Chin. Phys. B 17 3422
[4]	Chen Y C, Xie K, Pan Y, Zheng C M and Wang H L 2011 Chin. Phys. B 20 028201
[5]	Tarascon J M and Guyomard D 1993 Electrochim. Acta 38 1221
[6]	Guyomard D and Tarascon J M 1994 Solid State Ionics 69 222
[7]	Sun X, Yang X Q, Balasubramanian M, McBreen J, Xia Y and Sakai T 2002 J. Electrochem. Soc. 149 A842
[8]	Saitoh M, Sano M, Fujita M, Sakata M, Takata M and Nishibori E 2004 J. Electrochem. Soc. 151 A17
[9]	Tarascon J M, Mckinnon W R, Coowar F, Boowner T N, Amatucci G and Guyomard D 1997 J. Electrochem. Soc. 22 141
[10]	Yamaguchi H, Yamada A and Uwe H 1998 Phys. Rev. B 58 8
[11]	Choi W and Manthiram A 2006 J. Electrochem. Soc. 153 A1760
[12]	Thackeray M M 1997 Prog. Solid State Chem. 25 1
[13]	Arora P, Popov B and White R E 1998 J. Electrochem. Soc. 145 807
[14]	Takahashi M, Yoshida T, Ichikawa A, Kitoh K, Katsukawa H, Zhang Q and Yoshio M 2006 Electrochim. Acta 51 5508
[15]	Li G H, Ikuta H, Uchida T and Wakihara M 1996 J. Electrochem. Soc. 143 178
[16]	Zhong Q, Bonakdarpour A, Zhang M, Gao Y and Dahn J R 1997 J. Electrochem. Soc. 144 205
[17]	Ein-Eli Y, Howard W F, Lu S H, Mukerjee S, Mcbreen J, Vaughey J T and Thackeray M M 1998 J. Electrochem. Soc. 145 1238
[18]	Kim J H, Myung S T and Sun Y K 2004 Electrochim. Acta 49 219
[19]	Patoux S, Sannier L, Lignier H, Reynier Y, Bourbon C, Jouanneau S, Cras F L and Martinet S 2008 Electrochim. Acta 53 4137
[20]	Wang L P, Li H, Huang X J and Baudrin E 2011 Solid State Ionics 193 32
[21]	Blasse G 1966 J. Phys. Chem. Solids 27 383
[22]	Goodenough J B 1963 Magnetism and the Chemical Bond (New York: Wiley)
[23]	Branford W, Green M A and Neumann D A 2002 Chem. Mater. 14 1649
[24]	Lee Y J, Eng C and Grey C P 2001 J. Electrochem. Soc. 148 A249
[25]	Nakamura T, Yamada Y and Tabuchi M 2005 J. Appl. Phys. 98 093905
[26]	Amdouni N, Zaghib K, Gendron F, Mauger A and Julien C M 2007 J. Magn. Magn. Mater. 309 100
[27]	Kim J H, Myung S T, Yoon C S, Kang S G and Sun Y K 2004 Chem. Mater. 16 906
[28]	Kunduraci M and Amatucci G G 2006 J. Electrochem. Soc. 153 A1345
[29]	Kunduraci M, Al-Sharab J F and Amatucci G G 2006 Chem. Mater. 18 3585
[30]	Ariyoshi K, Iwakoshi Y, Nakayama N and Ohzuku T 2004 J. Electrochem. Soc. 151 A296
[31]	Shi S Q, Ouyang C Y, Wang D S, Chen L Q and Huang X J 2003 Solid State Commun. 126 531
[32]	Biškup N, Martínez J L, Arroyo Y, de Dompablo M E, Díaz-Carrasco P and Morales J 2006 J. Appl. Phys. 100 093908
[33]	Xia H, Meng Y S, Lu L and Ceder G 2007 J. Electrochem. Soc. 154 A737
[34]	Blöchl P E 1994 Phys. Rev. B 50 17953
[35]	Kresse G and Joubert D 1999 Phys. Rev. B 59 1758
[36]	Kresse G and Furthmüller J 1996 Comput. Mater. Sci. 6 15
[37]	Perdew J P, Chevary J A, Vosko S H, Jackson K A, Pederson M R, Singh D J and Fiolhais C 1992 Phys. Rev. B 46 6671
[38]	Dudarev S L, Botton G A, Savrasov S Y, Humphreys C J and Sutton A P 1998 Phys. Rev. B 57 1505
[39]	Zhou F, Kang K, Maxisch T, Ceder G and Morgan D 2004 Solid State Commun. 132 181
[40]	Ouyang C Y, Du Y L, Shi S Q and Lei M S 2009 Phys. Lett. A 373 2796
[41]	Methfessel M and Paxton A T 1989 Phys. Rev. B 40 3616
[42]	Blöchl P E, Jepsen O and Andersen O K 1994 Phys. Rev. B 49 16223
[43]	Takahashi K, Saitoh M, Sano M, Fujita M and Kifune K 2004 J. Electrochem. Soc. 151 A173
[44]	Alcántara R, Jaraba M, Lavela P, Tirado J L, Zhecheva E and Stoyanova R 2004 Chem. Mater. 16 1573
[45]	Wakihara M 2005 Electrochemistry (Tokyo, Jpn.) 73 328
[46]	Ammundsen B, Roziére J and Islam M S 1997 J. Phys. Chem. B 101 8156
[47]	Ma X H, Kang B and Ceder G 2010 J. Electrochem. Soc. 157 A925

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Structural and magnetic properties of LiNi0.5Mn1.5O4 and LiNi0.5Mn1.5O4-δ spinels: A first-principles study

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Structural and magnetic properties of LiNi_0.5Mn_1.5O₄ and LiNi_0.5Mn_1.5O_4-δ spinels: A first-principles study