Unraveling the doping mechanisms in lithium iron phosphate

Abstract

As a result of the extensive research and application of LiFePO₄ (LFP) in the past > 20 years, there is now a relatively in-depth understanding of its structural stability, phase transition mechanism and electrochemical properties. However, the difficulties faced by further improving the performance of LFP due to its intrinsic low electronic and ionic conductivity have not yet been effectively solved. In order to unlock the effect of transition metal doping on the physicochemical properties of LFP, we establish doping models for all 3d, 4d and 5d transition metals in LFP and compare and analyze their structural properties, band gaps, formation energies, elastic properties, anisotropies and lithiation/delithiation voltages using ab-initio computational screening. According to our screening results, the V-, Mn-, Ni-, Rh- and Os-doped LFP structures have excellent electrochemical properties and can be used as high-performance cathode materials for Li-ion batteries.

Keywords

LiFePO₄ / doping / computational screening / stability / cathode materials / lithium-ion batteries

References

[1] Padhi AK,Goodenough JB.Phospho-olivines as positive-electrode materials for rechargeable lithium batteries.J Electrochem Soc1997;144:1188-94

[2] Q; Advanced Batteries and Materials Engineering Research Center, Guizhou Light Industry Technical College, Guiyang 550025, China. Combined first-principles and experimental studies of a V- doped LiFePO₄/C composite as a cathode material for lithium-ion batteries.Int J Electrochem Sci2021;

[3] Zhang X,Shen Z.Green water-based binders for LiFePO ₄ /C cathodes in Li-ion batteries: a comparative study.New J Chem2021;45:9846-55

[4] Wang Y,Xue J,Liang G.LiFePO₄/C composites with high compaction density as cathode materials for lithium-ion batteries with high volumetric energy density.Ionics2021;27:4687-94

[5] Song Y,Song S.Regeneration of LiFePO ₄ from spent lithium-ion batteries via a facile process featuring acid leaching and hydrothermal synthesis.Green Chem2021;23:3963-71

[6] Huang X,Jiang C,Liu Y.Reaction mechanisms on solvothermal synthesis of nano LiFePO₄ crystals and defect analysis.Ind Eng Chem Res2017;56:10648-57

[7] Garay-marín JD,Garza-tovar LL.High-performing li-ion battery with “two cathodes in one” of sulfur and LiFePO₄ by strategies of mitigation of polysulfide shuttling.2021;4:359-67

[8] Cui Z,Ren J.Enhanced electrochemical performance and storage mechanism of LiFePO₄ doped by Co, Mn and S elements for lithium-ion batteries.Electrochimica Acta2021;388:138592

[9] Cheng Q,Yang G.Recent advances of metal phosphates-based electrodes for high-performance metal ion batteries.Energy Stor Mater2021;41:842-82

[10] Zhong Z,Zhu C,Kong L.Nano LiFePO₄ coated Ni rich composite as cathode for lithium ion batteries with high thermal ability and excellent cycling performance.J Power Sources2020;464:228235

[11] Nie Z,Yang L,Pan F.Construction and application of materials knowledge graph based on author disambiguation: revisiting the evolution of LiFePO₄.Adv Energy Mater2021;11:2003580

[12] Sifuba S,Feleni U,Iwuoha E.Electrochemical analysis of architecturally enhanced LiFe_0.5Mn_0.5PO₄ multiwalled carbon nanotube composite.J Nanotechnol2021;2021:1-8

[13] Sifuba S,Feleni U,Iwuoha E.Electrochemical analysis of architecturally enhanced LiFe_0.5Mn_0.5PO₄ multi-walled carbon nanotube composite.JNanoR2021;66:1-11

[14] Adepoju AA.High C-rate performance of LiFePO₄/carbon nanofibers composite cathode for Li-ion batteries.Curr Appl Phys2020;20:1-4

[15] Bazzi K,Dixit A.Nanostructured high specific capacity C-LiFePO₄ cathode material for lithium-ion batteries.J Mater Res2012;27:424-30

[16] Tian X,Jiang Z.Porous carbon-coated LiFePO₄ nanocrystals prepared by in situ plasma-assisted pyrolysis as superior cathode materials for lithium ion batteries.Ionics2020;26:2715-26

[17] Wang C,Tan H.Three-dimensional carbon-coated LiFePO₄ cathode with improved li-ion battery performance.Coatings2021;11:1137

[18] Yang G,He XM,Gao J.Preparation of Li₃V₂ (PO₄)₃/LiFePO₄ composite cathode material for lithium ion batteries.Ionics2013;19:1247-53

[19] Ren J,He X,Wan C.A carbon-LiFePO₄ nanocomposite as high-performance cathode material for lithium-ion batteries.Ionics2011;17:581-6

[20] Gao J,He XM,Wan CR.Synthesis and electrochemical characteristics of LiFePO₄/C cathode materials from different precursors.Int J Electrochem Sci2011;6(7):2818-2825. Available from:

[21] Gao Y,Zhang H.Effect of Ru doping on the properties of LiFePO₄/C cathode materials for lithium-ion batteries.ACS Omega2021;6:14122-9 PMCID:PMC8190806

[22] Liu Z,Wang D.First-principle investigations of N doping in LiFePO₄.Solid State Commun2008;147:505-9

[23] Yolun A,Altundag S,Abbas SM.Investigation of structural and electrochemical performance of Ru-substituted LiFePO₄ cathode material: an improvement of the capacity and rate performance.J Mater Sci: Mater Electron2022;33:6670-80

[24] Zhang L.Aluminium behaviour in preparation process of lithium iron phosphate and its effects on material electrochemical performance.J Mater Res Technol2021;15:3575-84

[25] Bai J,Chen H,Wang F.Solvothermal synthesis of LiMn_1- .x119:2266-76

[26] Li JG,Duan WL,Li JJ.Hydrothermal synthesis of well-dispersed LiMn_0.7Fe_0.3PO₄/C nanocrystalline cathodes for lithium-ion batteries.Int J Electrochem Sci2015;10(9):7371-7379. Available from:

[27] Ye F,He X.Solvothermal synthesis of nano LiMn_0.9Fe_0.1PO₄: reaction mechanism and electrochemical properties.J Power Sources2014;253:143-9

[28] Yang G,He X,Cai F.Preparation of V-LiFePO₄ cathode material for Li-ion batteries.Ionics2012;18:59-64

[29] Wang L,Li JJ,Jiang CY.First-principles study of doping in LiMnPO₄.Int J Electrochem Sci2012;7(4):3362-3370. Available from:

[30] Ying J,Jiang C.Preparation and characterization of high-density spherical Li_0.97Cr_0.01FePO₄/C cathode material for lithium ion batteries.J Power Sources2006;158:543-9

[31] Trinh DV,Dang HTM.Hydrothermally synthesized nanostructured LiMn_xFe_1-xPO₄ (x = 0-0.3) cathode materials with enhanced properties for lithium-ion batteries.Sci Rep2021;11:12280 PMCID:PMC8192943

[32] Zhang D,Dong K.First principles investigation on the elastic and electronic properties of Mn, Co, Nb, Mo doped LiFePO₄.Comput Mater Sci2018;155:410-5

[33] Wang D,Wang Z.Cracking causing cyclic instability of LiFePO₄ cathode material.J Power Sources2005;140:125-8

[34] Maxisch T.Elastic properties of olivine LixFePO4 from first principles.Phys Rev B2006;73

[35] Kobayashi H,Tabuchi M.Electrochemical properties of hydrothermally obtained LiCo[sub 1−x]Fe[sub x]O[sub 2] as a positive electrode material for rechargeable lithium batteries.J Electrochem Soc2000;147:960

[36] Needham S,Liu H,Liu R.Synthesis and electrochemical performance of doped LiCoO₂ materials.J Power Sources2007;174:828-31

[37] Kresse G.Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.Phys Rev B Condens Matter1996;54:11169-86

[38] Hafner J.Ab-initio simulations of materials using VASP: density-functional theory and beyond.J Comput Chem2008;29:2044-78

[39] Perdew JP,Ernzerhof M.Generalized Gradient Approximation Made Simple.Phys Rev Lett1996;77:3865-8

[40] Barma M.Gaussian smearing of spin weight functions in models of phase transitions.J Phys A: Math Gen1983;16:L745-50

[41] Yang L,Chen J.A high-rate capability LiFePO₄ /C cathode achieved by the modulation of the band structures.J Mater Chem A2021;9:24686-94

[42] Avilov A,Pietsch U.Multipole analysis of the electron density and electrostatic potential in germanium by high-resolution electron diffraction.J Phys Chem Solids2001;62:2135-42

[43] Shi S,Ouyang C.Enhancement of electronic conductivity of LiFePO₄ by Cr doping and its identification by first-principles calculations.Phys Rev B2003;68

[44] Zhang B,Song L,Fu X.Computational screening toward quantum capacitance of transition-metals and vacancy doped/co-doped graphene as electrode of supercapacitors.Electrochimica Acta2021;385:138432

[45] Zhang B,Song L.Computational screening toward hydrogen evolution reaction by the introduction of point defects at the edges of group IVA monochalcogenides: a first-principles study.J Phys Chem Lett2020;11:7664-71

[46] Xu CH,He XM,Shang YM.Formation mechanism and growth habit of olivine-LiFePO₄ materials by hydrothermal synthesis.Int J Electrochem Sci2016;11(2):1558-1567. Available from:

[47] de Walle CG, Neugebauer J. First-principles calculations for defects and impurities: Applications to III-nitrides.Journal of Applied Physics2004;95:3851-79

[48] Ko M,Jeong S,Cho J.Elastic a-silicon nanoparticle backboned graphene hybrid as a self-compacting anode for high-rate lithium ion batteries.ACS Nano2014;8:8591-9

[49] Chang B,Cho Y.Highly elastic binder for improved cyclability of nickel-rich layered cathode materials in lithium-ion batteries.Adv Energy Mater2020;10:2001069

[50] Zhang W,Guo Y.Tin-nanoparticles encapsulated in elastic hollow carbon spheres for high-performance anode material in lithium-ion batteries.Adv Mater2008;20:1160-5

[51] Chen Y,Anwar T.Application of galvanostatic intermittent titration technique to investigate phase transformation of LiFePO₄ nanoparticles.Electrochimica Acta2017;241:132-40

[52] Zhang B,Song L.Surface selectivity of Ni₃S₂ toward hydrogen evolution reaction: a first-principles study.Phys Chem Chem Phys2020;22:25685-94

[53] Güler E,Uğur Ş.DFT aspects of the elastic, mechanical, magnetic, thermodynamic and optical properties of Ce ₃ XY perovskites.Philos Mag2022;102:244-63

[54] Khanzadeh M.A DFT study on pressure dependency of TiC and ZrC properties: interconnecting elastic constants, thermodynamic, and mechanical properties.Ceram Int2021;47:9990-10005

[55] Chibani S,Arbouche O,Kafi A.Structural, elastic, electronic and transport properties of CoVX (X = Ge and Si) compounds: a DFT prediction.Computational Condensed Matter2020;24:e00475

[56] Hashigami S,Yoshimi K.Effect of lithium silicate addition on the microstructure and crack formation of LiNi_0.8Co_0.1Mn_0.1O₂ cathode particles.ACS Appl Mater Interfaces2019;11:39910-20

[57] Trevisanello E,Conforto G,Janek J.Polycrystalline and single crystalline NCM cathode materials-quantifying particle cracking, active surface area, and lithium diffusion.Adv Energy Mater2021;11:2003400

[58] Pang P,Wang Z.Crack-free single-crystal LiNi_0.83Co_0.10Mn_0.07O₂ as cycling/thermal stable cathode materials for high-voltage lithium-ion batteries.Electrochimica Acta2021;365:137380

[59] Kumberg J,Diehm R.Drying of lithium-ion battery anodes for use in high-energy cells: influence of electrode thickness on drying time, adhesion, and crack formation.Energy Technol2019;7:1900722