Evaluation of Olivine LiFePO₄ Polyanionic Cathode Material Using Density Functional Theory

Abstract:

The first principles study on the LiFePO₄ and FePO₄ crystal has been evaluated using the density functional theory encrypted in the Cambridge Serial Total Energy Package (CASTEP) computer code. The structural properties, electronic properties, and intercalation voltage of the cathode material are presented. Without the Hubbard U parameter, the conventional functional of GGA-PBE and GGA-PBEsol unable to produce the experimental open-circuit voltage (OCV) and band gap (BG) of cathode material correctly. Generally, the value of the lattice parameter, OCV, and BG will increase as the U value is increased. For OCV, the suitable U value for the GGA-PBE and GGA-PBEsol is 3 eV, whereas, for BG, the appropriate U value for both functional is around 4.3 eV to 4.5 eV. Different Hubbard U value is needed for different functional. It is found that GGA-PBEsol + U is the best parameter to calculate the electrical properties of LiFePO_{4 ­­­­}material.

• Periodical: Key Engineering Materials (Volume 908)
• Pages: 293-298
• DOI: https://doi.org/10.4028/p-csw2yc
• Online since: January 2022
• Authors: Shahrul Izwan Ahmad, Fadhlul Wafi Badrudin*, Abqari Luthfi Albert Abdullah, Muhd Zu Azhan Yahya, Mohamad Fariz Mohamad Taib, Oskar Hasdinor Hassan
• Keywords: CASTEP, Cathode Materials, Density Functional Theory, Lithium-Ion Battery

References

[1] H. Yan, B. Li, Z. Yu, W. Chu, D. Xia, First-Principles Study: Tuning the Redox Behavior of Lithium-Rich Layered Oxides by Chlorine Doping, J. Phys. Chem. C. 121 (2017) 7155–7163.

DOI: 10.1021/acs.jpcc.7b01168

[2] Y. Ding, Z.P. Cano, A. Yu, J. Lu, Z. Chen, Automotive Li-Ion Batteries: Current Status and Future Perspectives, Electrochem. Energy Rev. 2 (2019) 1–28.

DOI: 10.1007/s41918-018-0022-z

[3] A. Bhandari, J. Bhattacharya, R.G.S. Pala, Adsorption Preference of HF over Ethylene Carbonate Leads to Dominant Presence of Fluoride Products in LiFePO4 Cathode-Electrolyte Interface in Li-Ion Batteries, J. Phys. Chem. C. 124 (2020) 9170–9177.

DOI: 10.1021/acs.jpcc.0c00565

[4] J. Hu, W. Huang, L. Yang, F. Pan, Structure and performance of the LiFePO4cathode material: From the bulk to the surface, Nanoscale. 12 (2020) 15036–15044.

DOI: 10.1039/d0nr03776a

[5] A.K. Padhi, K.S. Nanjundaswamy, J.B. Goodenough, Phospho-olivines as Positive Electrode Materials for Rechargeable Lithium Batteries, J. Electrochem. Soc. 144 (1997) 1188–1194.

DOI: 10.1149/1.1837571

[6] M. Molenda, M. Świętosławski, A. Milewska, M.M. Zaitz, A. Chojnacka, B. Dudek, R. Dziembaj, Carbon nanocoatings for C/LiFePO4 composite cathode, Solid State Ionics. 251 (2013) 47–50.

DOI: 10.1016/j.ssi.2013.03.003

[7] J. Zhou, B.H. Liu, Z.P. Li, Nanostructure optimization of LiFePO4/carbon aerogel composites for performance enhancement, Solid State Ionics. 244 (2013) 23–29.

DOI: 10.1016/j.ssi.2013.05.003

[8] F.W. Badrudin, M.F.M. Taib, R.I.P.R. Mustapha, O.H. Hassan, M.Z.A. Yahya, Effects of Vanadium Substitution in the Layered LiFeSO4OH: A First Principles Investigation, Mater. Today Proc. 4 (2017) 5108–5115.

DOI: 10.1016/j.matpr.2017.05.015

[9] X. Wu, F. Kang, W. Duan, J. Li, Density functional theory calculations: A powerful tool to simulate and design high-performance energy storage and conversion materials, Prog. Nat. Sci. Mater. Int. 29 (2019) 247–255.

DOI: 10.1016/j.pnsc.2019.04.003

[10] Stewart J. Clark, M.D. Segall, C.J. Pickard, P.J. Hasnip, M.I.J. Probert, K. Refson, M.C. Payne, First principles methods using CASTEP, Zeitschrift Für Krist. 220 (2005) 567.

DOI: 10.1524/zkri.220.5.567.65075

[11] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized Gradient Approximation Made Simple, Phys. Rev. Lett. 77 (1996) 3865–3868.

DOI: 10.1103/physrevlett.77.3865

[12] J.P. Perdew, A. Ruzsinszky, G.I. Csonka, O.A. Vydrov, G.E. Scuseria, L.A. Constantin, X. Zhou, K. Burke, Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces, Phys. Rev. Lett. 100 (2008) 136406.

DOI: 10.1103/physrevlett.102.039902

[13] H.J. Monkhorst, J.D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B. 13 (1976) 5188–5192.

DOI: 10.1103/physrevb.13.5188

[14] J. Jung, M. Cho, M. Zhou, Ab initio study of the fracture energy of LiFePO4/FePO4 interfaces, J. Power Sources. 243 (2013) 706–714.

DOI: 10.1016/j.jpowsour.2013.06.030

[15] H. Lin, Y. Wen, C. Zhang, L. Zhang, Y. Huang, B. Shan, R. Chen, A GGA+U study of lithium diffusion in vanadium doped LiFePO4, Solid State Commun. 152 (2012) 999–1003.

DOI: 10.1016/j.ssc.2012.03.027

[16] C. Loschen, J. Carrasco, K.M. Neyman, F. Illas, First-principles LDA+U and GGA+U study of cerium oxides: Dependence on the effective U parameter, Phys. Rev. B - Condens. Matter Mater. Phys. 75 (2007) 35115.

DOI: 10.1103/physrevb.84.199906

[17] M. Aydinol, A. Kohan, G. Ceder, K. Cho, J. Joannopoulos, Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides, Phys. Rev. B - Condens. Matter Mater. Phys. 56 (1997) 1354–1365.

DOI: 10.1103/physrevb.56.1354

[18] F.W. Badrudin, M.F.M. Taib, O.H. Hassan, M.Z.A. Yahya, Effect of lithium intercalation on the structural and electronic properties of layered LiFeSO4OH and layered FeSO4OH using first-principle calculations, Comput. Mater. Sci. 119 (2016) 144–151.

DOI: 10.1016/j.commatsci.2016.03.042

[19] S. Laref, A. Laref, Theoretical insight into the strain effect on the intercalation potential of Li-FePO4 materials, RSC Adv. 5 (2015) 35667–35674.

DOI: 10.1039/c5ra00045a

[20] F. Zhou, M. Cococcioni, K. Kang, G. Ceder, The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M = Fe, Mn, Co, Ni, Electrochem. Commun. 6 (2004) 1144–1148.

DOI: 10.1016/j.elecom.2004.09.007

[21] Y. Okuno, K. Ushirogata, K. Sodeyama, G. Shukri, Y. Tateyama, Structures, Electronic States, and Reactions at Interfaces between LiNi 0.5 Mn 1.5 O 4 Cathode and Ethylene Carbonate Electrolyte: A First-Principles Study, J. Phys. Chem. C. 123 (2019) 2267–2277.

DOI: 10.1021/acs.jpcc.8b10625

[22] S. Shi, L. Liu, C. Ouyang, D.S. Wang, Z. Wang, L. Chen, X. Huang, Enhancement of electronic conductivity of LiFePO4 by Cr doping and its identification by first-principles calculations, Phys. Rev. B - Condens. Matter Mater. Phys. 68 (2003) 1951081–1951085.

DOI: 10.1103/physrevb.68.195108

[23] Y.-N. Xu, S.-Y. Chung, J.T. Bloking, Y.-M. Chiang, W.Y. Ching, Electronic Structure and Electrical Conductivity of Undoped LiFePO4, Electrochem. Solid-State Lett. 7 (2004) A131–A134.

DOI: 10.1149/1.1703470

[24] P. Tang, N.A.W. Holzwarth, Electronic structure of FePO4, LiFePO4, and related materials, Phys. Rev. B. 68 (2003) 165107.

[25] C. Frayret, A. Villesuzanne, N. Spaldin, E. Bousquet, J.-N. Chotard, N. Recham, J.-M. Tarascon, LiMSO4F (M = Fe, Co and Ni): promising new positive electrode materials through the DFT microscope., Phys. Chem. Chem. Phys. 12 (2010) 15512–22.

DOI: 10.1039/c0cp00517g

[26] T. Tsevelmaa, D. Odkhuu, O. Kwon, S. Cheol Hong, A first-principles study of magnetism of lithium fluorosulphate LiFeSO4F, J. Appl. Phys. 113 (2013) 17B302.

DOI: 10.1063/1.4794723

[27] A.K. Padhi, V. Manivannan, J.B. Goodenough, Tuning the Position of the Redox Couples in Materials with NASICON Structure by Anionic Substitution, J. Electrochem. Soc. 145 (1998) 1518–1520.

DOI: 10.1149/1.1838513

[28] D.-H. Seo, Y.-U. Park, S.-W. Kim, I. Park, R. a. Shakoor, K. Kang, First-principles study on lithium metal borate cathodes for lithium rechargeable batteries, Phys. Rev. B. 83 (2011) 205127.

DOI: 10.1103/physrevb.83.205127

[29] F. Zhou, K. Kang, T. Maxisch, G. Ceder, D. Morgan, The electronic structure and band gap of LiFePO4 and LiMnPO4, Solid State Commun. 132 (2004) 181–186.

DOI: 10.1016/j.ssc.2004.07.055