Comparative study on electronic structures of two phases compounds and origin of the structural phase transition in LiFePO4

doi:10.1088/1674-1056/ae0bfe

Abstract LiFePO$_{4}$ has normal olivine-structured ($\alpha $-LFP) and high pressure ($\beta $-LFP) phases, with the former being one of the cathode materials for commercial Li-ion batteries. Despite extensive focus on the respective electrochemical properties of the two phases, there is a lack of comparative studies on their electronic and magnetic properties, and the origin of the structural phase transition remains unclear. By combining first-principles calculations with molecular dynamics simulations, we find that the anisotropic compression of Li—O bonds drives the structural phase transition from $\alpha $-LFP to $\beta $-LFP at a critical pressure of 20 GPa, while $\beta $-LFP undergoes a transition from semiconductor to metal due to Fe$^{3+}$ generated during delithiation. Their antiferromagnetic (AFM) ground states are predicted to arise from the negative magnetic exchange interactions between nearest and next-nearest neighbor sites, with the corresponding Néel temperature showing significant enhancement under pressure. Furthermore, compared with $\alpha $-LFP, $\beta $-LFP shows increases in bulk, shear, and Young's moduli of 8%, 13%, and 12%, respectively. These findings enrich the physical property data of LiFePO$_{4}$ phase compounds, providing knowledge for expanding the application scenarios of the $\alpha $-LFP phase under special operating conditions such as high pressure.

Keywords: lithium-ion battery LiFePO₄ structural phase transition first-principles calculations

Received: 16 July 2025
Revised: 15 September 2025
Accepted manuscript online: 26 September 2025

PACS:	82.47.Aa	(Lithium-ion batteries)
	63.20.dk	(First-principles theory)

Fund: Project supported by the National Natural Science Foundation of China (Grant No. 12304089) and the start-up foundation from Shanghai University. Calculations were partially performed on computers at the Shanghai Technical Service Center for Scientific and Engineering Computing, Shanghai University.

Corresponding Authors: Jie Li, Siqi Shi
E-mail: lij@shu.edu.cn;sqshi@shu.edu.cn

Cite this article:

Peiru Yang(杨佩如), Xinchun Du(杜新春), Jie Li(李杰), Siqi Shi(施思齐) Comparative study on electronic structures of two phases compounds and origin of the structural phase transition in LiFePO₄ 2025 Chin. Phys. B 34 118201

[1] Albertus P, Anandan V, Ban C, et al. 2021 ACS Energy Lett. 6 1399
[2] Tao R, Gu Y, Du Z, Lyu X and Li J 2025 Nat. Rev. Clean Technol. 1 116
[3] Li L,Wu L,Wu F, Song S, Zhang X, Fu C, Yuan D and Xiang Y 2017 J. Electrochem. Soc. 164 A2138
[4] He J, Meng J and Huang Y 2023 J. Power Sources 570 232965
[5] Padhi A K, Nanjundaswamy K S and Goodenough J B 1997 J. Electrochem. Soc. 144 1188
[6] Yamada A, Chung S C and Hinokuma K 2001 J. Electrochem. Soc. 148 A224
[7] Liu H, Strobridge F C, Borkiewicz O J,Wiaderek K M, Chapman KW, Chupas P J and Grey C P 2014 Science 344 1252817
[8] Wang W, Wang R, Zhan R, Du J, Chen Z, Feng R, Tan Y, Hu Y, Ou Y, Yuan Y, Li C, Xiao Y and Sun Y 2023 Nano Lett. 23 7485
[9] Zhao X,Wang X, Guo J, Gu Z, Cao J, Yang J, Lu F, Zhang J andWu X 2024 Adv. Mater. 36 2308927
[10] Cao M, Liu Z, Zhang X, Yang L, Xu S, Weng S, Zhang S, Li X, Li Y, Liu T, Gao Y, Wang X, Wang Z and Chen L 2023 Adv. Funct. Mater. 33 2210032
[11] Chung S, Bloking J and Chiang Y 2002 Nat. Mater. 1 123
[12] Ouyang C, Wang D, Shi S, Wang Z, Li H, Huang X and Chen L 2006 Chin. Phys. Lett. 23 61
[13] Shi S, Liu L, Ouyang C, Wang D, Wang Z, Chen L and Huang X 2003 Phys. Rev. B 68 195108
[14] Li H, Wang Z, Chen L and Huang X 2009 Adv. Mater. 21 4593
[15] Li Z, Zhang D and Yang F 2009 J. Mater. Sci. 44 2435
[16] Andersson A S and Thomas J O 2001 J. Power Sources 97 498
[17] Gai J, Yang J, Yang W, Li Q, Wu X and Li H 2023 Chin. Phys. Lett. 40 086101
[18] Li Y, Sun S, He Y and Li H 2022 Chin. Phys. Lett. 39 026101
[19] Du J, Tao H, Chen Y, Yuan X, Lian C and Liu H 2021 Chin. Phys. Lett. 38 118201
[20] Axmann P, Stinner C, Wohlfahrt-Mehrens M, Mauger A, Gendron F and Julien C 2009 Chem. Mater. 21 1636
[21] García-Moreno O, Alvarez-Vega M, García-Alvarado F, García-Jaca J, Gallardo-Amores J, Sanjuán M and Amador U 2001 Chem. Mater. 13 1570
[22] Lin H and Zeng Z 2011 IEEE Trans. Magn. 47 3817
[23] Dong H, Guo H, He Y, Gao J, HanW, Lu X, Yan S, Yang K, Li H, Chen D and Li H 2017 Solid State Ion. 301 133
[24] Wu C, Huang W, Liu L, Wang H, Zeng Y, Xie J, Jin C and Zhang Z 2016 CrystEngComm 18 7707
[25] Guo H, Song X, Zhuo Z, Hu J, Liu T, Duan Y, Zheng J, Chen Z, Yang W, Amine K and Pan F 2016 Nano Lett. 16 601
[26] Hohenberg P and Kohn W 1964 Phys. Rev. 136 B864
[27] Kresse G and Furthmüler J 1996 Phys. Rev. B 54 11169
[28] Liechtenstein A I, Anisimov V I and Zaanen J 1995 Phys. Rev. B 52 R5467
[29] Henkelman G, Uberuaga B P and Jónsson H 2000 J. Chem. Phys. 113 9901
[30] Parrinello M and Rahman A 1980 Phys. Rev. Lett. 45 1196
[31] Ouyang C, Shi S, Wang Z, Huang X and Chen L 2004 Phys. Rev. B 69 104303
[32] Pei B, Yao H, Zhang W and Yang Z 2012 J. Power Sources 220 317
[33] Maxisch T and Ceder G 2006 Phys. Rev. B 73 174112
[34] Zhang Z, Ma H and Wan B 2024 JOM 77 2943
[35] Zeng G, Caputo R, Carriazo D, Luo L and NiederbergerM2013 Chem. Mater. 25 3399
[36] Fisher C A J, Hart Prieto V M and Islam M S 2008 Chem. Mater. 20 5907
[37] Adams S and Prasada Rao R 2011 Solid State Ion. 184 57
[38] Santoro R and Newnham R 1967 Acta Cryst. 22 344
[39] Li J, Garlea V, Zarestky J and Vaknin D 2006 Phys. Rev. B 73 0234410
[40] Werner J, Neef C, Koo C, Zvyagin S, Ponomaryov A and Klingeler R 2020 Phys. Rev. Mater. 4 115403
[41] Shi S, Ouyang C, Xiong Z, Liu L, Wang Z, Li H, Wang D, Chen L and Huang X 2005 Phys. Rev. B 71 144404
[42] Zhang Y, Alarco J, Best A, Snook G, Talbot P and Nerkar J 2019 RSC Adv. 9 1134

[1]	Site occupation of Al doping in Lu₂SiO₅: The role of ionic radius versus chemical valence Xuejiao Sun(孙雪娇), Yu Cui(崔宇), Feng Gao(高峰), Zhongjun Xue(薛中军), Shuwen Zhao(赵书文), Dongzhou Ding(丁栋舟), Fan Yang(杨帆), and Yi-Yang Sun(孙宜阳). Chin. Phys. B, 2025, 34(9): 096101.
[2]	Superconductivity and band topology of double-layer honeycomb structure M₂N₂ (M = Nb, Ta) Jin-Han Tan(谭锦函), Na Jiao(焦娜), Meng-Meng Zheng(郑萌萌), Ping Zhang(张平), and Hong-Yan Lu(路洪艳). Chin. Phys. B, 2025, 34(9): 097402.
[3]	Doping-induced magnetic and topological transitions in Mn₂X₂Te₅ (X = Bi, Sb) bilayers Wei Chen(陈威), Chuhan Tang(唐楚涵), Chao-Fei Liu(刘超飞), and Mingxing Chen(陈明星). Chin. Phys. B, 2025, 34(9): 097304.
[4]	First-principles calculations on strain tunable hyperfine Stark shift of shallow donors in Si Zi-Kai Zhou(周子凯) and Jun Kang(康俊). Chin. Phys. B, 2025, 34(8): 087102.
[5]	Unveiling the role of high-order anharmonicity in thermal expansion: A first-principles perspective Tianxu Zhang(张天旭), Kun Zhou(周琨), Yingjian Li(李英健), Chenhao Yi(易晨浩), Muhammad Faizan, Yuhao Fu(付钰豪), Xinjiang Wang(王新江), and Lijun Zhang(张立军). Chin. Phys. B, 2025, 34(4): 046301.
[6]	Emergence of metal-semiconductor phase transition in MX₂(M = Ni, Pd, Pt; X = S, Se, Te) moiré superlattices Jie Li(李杰), Rui-Zi Zhang(张瑞梓), Jinbo Pan(潘金波), Ping Chen(陈平), and Shixuan Du(杜世萱). Chin. Phys. B, 2025, 34(3): 037302.
[7]	Phonon-mediated superconductivity in orthorhombic XS (X = Nb, Ta or W) Guo-Hua Liu(刘国华), Kai-Yue Jiang(江恺悦), Yi Wan(万一), Shu-Xiang Qiao(乔树祥), Jin-Han Tan(谭锦函), Na Jiao(焦娜), Ping Zhang(张平), and Hong-Yan Lu(路洪艳). Chin. Phys. B, 2025, 34(2): 027401.
[8]	Stable structures and properties of Ru₂Al₅ Jing Luo(罗晶), Meiguang Zhang(张美光), Xiaofei Jia(贾晓菲), and Qun Wei(魏群). Chin. Phys. B, 2025, 34(1): 016301.
[9]	Two-dimensional Cr₂Cl₃S₃ Janus magnetic semiconductor with large magnetic exchange interaction and high-T_C Lei Fu(伏磊), Shasha Li(李沙沙), Xiangyan Bo(薄祥䶮), Sai Ma(马赛), Feng Li(李峰), and Yong Pu(普勇). Chin. Phys. B, 2024, 33(9): 096301.
[10]	Strain-tuned electronic and valley-related properties in Janus monolayers of SWSiX₂ (X = N, P, As) Yunxi Qi(戚云西), Jun Zhao(赵俊), and Hui Zeng(曾晖). Chin. Phys. B, 2024, 33(9): 096302.
[11]	Alternating spin splitting of electronic and magnon bands in two-dimensional altermagnetic materials Qian Wang(王乾), Da-Wei Wu(邬大为), Guang-Hua Guo(郭光华), Meng-Qiu Long(龙孟秋), and Yun-Peng Wang(王云鹏). Chin. Phys. B, 2024, 33(9): 097507.
[12]	Electronic transport evolution across the successive structural transitions in Ni_50-xFe_xTi₅₀ shape memory alloys Ping He(何萍), Jinying Yang(杨金颖), Qiusa Ren(任秋飒), Binbin Wang(王彬彬), Guangheng Wu(吴光恒), and Enke Liu(刘恩克). Chin. Phys. B, 2024, 33(7): 077201.
[13]	Non-Kramers doublet ground state in a quaternary cubic compound PrRu₂In₂Zn₁₈ investigated by ultrasonic measurements Hua-Yuan Zhang(张化远), Kazuhei Wakiya, Mitsuteru Nakamura, Masahito Yoshizawa, and Yoshiki Nakanish. Chin. Phys. B, 2024, 33(6): 064301.
[14]	Regulating the dopant clustering in LiZnAs-based diluted magnetic semiconductor Zihang Jia(贾子航), Bo Zhou(周波), Zhenyi Jiang(姜振益), and Xiaodong Zhang(张小东). Chin. Phys. B, 2024, 33(5): 058101.
[15]	Spin direction dependent quantum anomalous Hall effect in two-dimensional ferromagnetic materials Yu-Xian Yang(杨宇贤) and Chang-Wen Zhang(张昌文). Chin. Phys. B, 2024, 33(4): 047101.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Metrics
Related Articles

Comparative study on electronic structures of two phases compounds and origin of the structural phase transition in LiFePO4

Cite this article:

Online attention

Comparative study on electronic structures of two phases compounds and origin of the structural phase transition in LiFePO₄