Evaluating Electrical Properties, Band Gaps and Rate Capability of Li2MSiO4 (M= Mn, Fe, Co, Ni) Cathode Materials Using DOS Diagrams

Document Type : Original Research Article

Authors

Department of Ceramic, Materials and Energy Research Center, Meshkindasht, Alborz, Iran

Abstract

In this study, theoretical investigations of Li2MSiO4 family cathode materials, including Li2MnSiO4, Li2FeSiO4, Li2CoSiO4, and Li2NiSiO4 are performed using density functional theory (DFT), by GGA and GGA+U methods. The materials properties including electrical conductivity and rate capability were investigated. To evaluate electrical conductivity, we use here a noble approach in DFT established in our previous work, which is related to intrinsic/extrinsic band gap concepts in solid state physics. Also, using lithiated-delithiated junction, aligning Fermi levels, and the difference between conduction bands value is the basis of the comparison of                      rate-capability, which is also a noble approach. To perform a quantitative investigation of electrical rate-capability, Fermi levels of obtained DOS diagrams of lithiated and delithiated structures were aligned. The difference between maximum of valance band (MVB) of lithiated and delithiated structures was considered as the criteria of rate-capability. The obtained values for the considered materials were fairly close. It was concluded that electron conductivity and rate-capability of this family of Li-ion cathode material is in the same range and do not strictly relate to the transition metal.

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1.       Kalantarian, M. M., Asgari, S., Capsoni, D., Mustarelli, P., "An ab initio investigation of Li2M0.5N0.5SiO4 (M, N= Mn, Fe, Co Ni) as Li-ion battery cathode materials", Physical Chemistry Chemical Physics, Vol. 15, No. 21, (2013), 8035-8041.
2.       Kalantarian, M. M., Asgari, S., "Theoretical Assessment of the First Cycle Transition, Structural Stability and Electrochemical Properties of Li2FeSiO4 as a Cathode Material for Li-ion Battery", Advanced Ceramics Progress, Vol. 3, No.  4, (2017), 25-33.
3.       Kalantarian, M. M., Oghbaei, M., Asgari, S., Karimi, L., Ferrari, S., Capsoni, D., Bini, M., Mustarelli, P., "Electrochemical Characterization of Low-Cost Lithium-Iron Orthosilicate Samples as Cathode Materials of Lithium-Ion Battery", Advanced Ceramics Progress, Vol. 3, No. 3, (2017), 19-25.
4.       Kalantarian, M. M., Asgari, S., Mustarelli, P., "Theoretical investigation of Li2MnSiO4 as a cathode material for Li-ion batteries: a DFT study", Journal of Materials Chemistry A, Vol. 1, No. 8, (2013), 2847-2855.
5.       Kalantarian, M. M., Asgari, S., Mustarelli, P., "A theoretical approach to evaluate the rate capability of Li-ion battery cathode materials", Journal of Materials Chemistry A, Vol. 2, No. 1, (2014), 107-115.
6.       Zhou, F., Cococcioni, M., Kang, K., Ceder, G., "The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M= Fe, Mn, Co, Ni", Electrochemistry Communications, Vol. 6, No. 11, (2004), 1144-1148.
7.       Guo, H.-J. Xiang, K.X., Xuan, C.A.O., Li, X.H., Wang, Z.X., Li, L.M., "Preparation and characteristics of Li2FeSiO4/C composite for cathode of lithium ion batteries", Transactions of Nonferrous Metals Society of China, Vol. 19,  No. 1, (2009), 166-169.
8.       Kazazi, M., Illbeigi, M., Fazlali, A. & Mohammadi, A., "Preparation, characterization and stability of Li-ion conducting Li1.5Al0.5Ge1.5(PO4)3 glass-ceramic with NASICON-type structure", Advanced Ceramics Progress, Vol. 2, No. 1, (2016), 38-43.
9.       Dahbi, M., Urbonaite, S., Gustafsson, T., "Combustion synthesis and electrochemical performance of Li2FeSiO4/C cathode material for lithium-ion batteries", Journal of Power Sources, Vol. 205, (2012), 456-462.
10.    Zhang, S., Deng, C., Fu, B., Yang, S., Ma, L., "Effects of Cr doping on the electrochemical properties of Li2FeSiO4 cathode material for lithium-ion batteries", Electrochimica Acta, Vol. 55, No. 28, (2010), 8482-8489.
11.    Dominko, R., Bele, M., Kokalj, A., Gaberscek, M., Jamnik, J., "Li2MnSiO4 as a potential Li-battery cathode material", Journal of Power Sources, Vol. 174, No. 2, (2007), 457-461.
12.    Gummow, R., Sharma, N., Peterson, V., He, Y., "Synthesis, structure, and electrochemical performance of magnesium-substituted lithium manganese orthosilicate cathode materials for lithium-ion batteries", Journal of Power Sources, Vol. 197, (2012), 231-237.
13.    Gong, Z., Li, Y., Yang, Y., "Synthesis and electrochemical performance of Li2CoSiO4 as cathode material for lithium ion batteries", Journal of Power Sources, Vol. 174, No. 2, (2007), 524-527.
14.    Wu, S. Q., Zhang, J. H., Zhu, Z. Z., Yang, Y., "Structural and electronic properties of the Li-ion battery cathode material LixCoSiO4", Current Applied Physics, Vol. 7, No. 6, (2007), 611-616.
15.    Kalantarian, M. M., Oghbaei, M., Asgari, S., Ferrari, S., Capsoni, D., Mustarelli, P., "Understanding non-ideal voltage behaviour of cathodes for lithium-ion batteries", Journal of Materials Chemistry A, Vol. 2, No. 45, (2014), 19451-19460.
16.    Momeni, M., Mashhour, H. Y., Kalantarian, M. M., "New approaches to consider electrical properties, band gaps and rate capability of same-structured cathode materials using density of states diagrams: Layered oxides as a case study", Journal of Alloys and Compounds, Vol. 787, (2019), 738-743.
17.    Perdew, J. P., Yang, W., Burke, K., Yang, Z., Gross, E.K., Scheffler, M., Scuseria, G.E., Henderson, T.M., Zhang, I.Y., Ruzsinszky, A., Peng, H., "Understanding band gaps of solids in generalized Kohn–Sham theory", Proceedings of the National Academy of Sciences, Vol. 114, No. 11, (2017), 2801-2806.
18.    Nytén, A., Abouimrane, A., Armand, M., Gustafsson, T., Thomas, J. O., "Electrochemical performance of Li2FeSiO4 as a new Li-battery cathode material", Electrochemistry Communications, Vol. 7, No. 2, (2005), 156-160.
19.    Nytén, A., Kamali, S., Häggström, L., Gustafsson, T., Thomas, J. O., "The lithium extraction/insertion mechanism in Li2FeSiO4", Journal of Materials Chemistry, Vol. 16, No. 23, (2006), 2266-2272.
20.    Perdew, J. P., "k. Burke, m. ernzerhof", Physical Review Letters, Vol. 77, (1996), 3865.
21.    Delmas, C., Maccario, M., Croguennec, L., Le Cras, F., Weill, F., "Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascademodel" in Materials For Sustainable Energy: A Collection of Peer-Reviewed Research and Review Articles from Nature Publishing Group, (2011), 180-186.
22.    Wang, J., Chen-Wiegart, Y.C. K., Wang, J., "In operando tracking phase transformation evolution of lithium iron phosphate with hard X-ray microscopy", Nature communications, Vol. 5, (2014), 4570.
23.    Zhu, H., Wu, X., Zan, L., Zhang, Y., "Superior electrochemical capability of Li2FeSiO4/C/G composite as cathode material for Li-ion batteries", Electrochimica Acta, Vol. 117, (2014), 34-40.