Lattice engineering of high-entropy olivine-type lithium metal phosphate as high-voltage cathodes

Fan, Juntian; Wang, Tao; Yuan, Yating; Borisevich, Albina; Do-Thanh, Chi-Linh; Yang, Zhenzhen; Dai, Sheng

doi:10.1063/5.0201709

Title: Lattice engineering of high-entropy olivine-type lithium metal phosphate as high-voltage cathodes

Journal Article · 25 April 2024 · Applied Physics Letters

DOI: https://doi.org/10.1063/5.0201709 · OSTI ID:2349202

^[1];

^[1]; Yuan, Yating ^[1];

^[2];

^[3]; Yang, Zhenzhen ^[1];

^[4]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
University of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; University of Tennessee, Knoxville, TN (United States)

Engineering of high-entropy cathode materials for lithium-ion batteries has been actively pursued owing to the outstanding conductivity of high-entropy materials benefited from the maximum entropy and unique antisite disordering structure. Olivine lithium metal phosphates such as LiMnPO₄ and LiNiPO₄ feature high working voltages but low capacities due to their insulation nature. Here in this work, the synthesis of the high-entropy lithium metal phosphate materials (HELMPs) is realized by combining mechanochemistry with a calcination method. By regulating lattice of HELMPs, the high-entropy Li(Mn_0.35Fe_0.35Co0.1Mg_0.1Ca_0.1)PO₄ reveals three typical high-voltage plateaus in charge–discharge curves corresponding to the redox of Fe, Mn, and Co in the voltage range of 2.0–4.9 V vs Li⁺/Li, and a much higher initial capacity than LiMnPO₄ (104 vs 15 mAh g^-1).

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2349202

Journal Information:: Applied Physics Letters, Journal Name: Applied Physics Letters Journal Issue: 17 Vol. 124; ISSN 0003-6951

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

High-Performance Olivine for Lithium Batteries: Effects of Ni/Co Doping on the Properties of LiFe _α Ni _β Co _γ PO ₄ Cathodes Pagot, Gioele; Bertasi, Federico; Nawn, Graeme Advanced Functional Materials, Vol. 25, Issue 26 https://doi.org/10.1002/adfm.201501167	journal	May 2015
Layer‐Based Heterostructured Cathodes for Lithium‐Ion and Sodium‐Ion Batteries Deng, Ya‐Ping; Wu, Zhen‐Guo; Liang, Ruilin Advanced Functional Materials, Vol. 29, Issue 19 https://doi.org/10.1002/adfm.201808522	journal	February 2019
Mechanochemical-Assisted Synthesis of High-Entropy Metal Nitride via a Soft Urea Strategy Jin, Tian; Sang, Xiahan; Unocic, Raymond R. Advanced Materials, Vol. 30, Issue 23 https://doi.org/10.1002/adma.201707512	journal	April 2018
High‐Entropy Metal–Organic Frameworks for Highly Reversible Sodium Storage Ma, Yanjiao; Ma, Yuan; Dreyer, Sören Lukas Advanced Materials, Vol. 33, Issue 34 https://doi.org/10.1002/adma.202101342	journal	July 2021
High‐Entropy Layered Oxide Cathodes for Sodium‐Ion Batteries Zhao, Chenglong; Ding, Feixiang; Lu, Yaxiang Angewandte Chemie International Edition, Vol. 59, Issue 1 https://doi.org/10.1002/anie.201912171	journal	January 2020
Perovskite Oxide–Halide Solid Solutions: A Platform for Electrocatalysts Wang, Tao; Fan, Juntian; Do‐Thanh, Chi‐Linh Angewandte Chemie International Edition, Vol. 60, Issue 18 https://doi.org/10.1002/anie.202101120	journal	March 2021
Effect of manganese doping on conduction in olivine LiFePO4 Gupta, Reema; Saha, Shibu; Tomar, Monika Journal of Materials Science: Materials in Electronics, Vol. 28, Issue 7 https://doi.org/10.1007/s10854-016-6175-9	journal	December 2016
Vibrational studies of olivine-type compounds—II Orthophosphates, -arsenates and -vanadates AIBIIXVO4 Paques-Ledent, M. Th.; Tarte, P. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 30, Issue 3 https://doi.org/10.1016/0584-8539(74)80190-X	journal	March 1974
Positive effects of a particular type of microwave-assisted methodology on the electrochemical properties of olivine LiMPO4 (M= Fe, Co and Ni) cathode materials Örnek, Ahmet Chemical Engineering Journal, Vol. 331 https://doi.org/10.1016/j.cej.2017.09.007	journal	January 2018
Li(Ni,Co)PO4 as cathode materials for lithium batteries: Will the dream come true? Mauger, A.; Julien, C. M.; Armand, M. Current Opinion in Electrochemistry, Vol. 6, Issue 1 https://doi.org/10.1016/j.coelec.2017.10.015	journal	December 2017
Recent advancements in LiCoPO4 cathodes using electrolyte additives Sreedeep, Sreekumar; Natarajan, Subramanian; Aravindan, Vanchiappan Current Opinion in Electrochemistry, Vol. 31 https://doi.org/10.1016/j.coelec.2021.100868	journal	February 2022
Seeking direct cathode regeneration for more efficient lithium-ion battery recycling Gao, Hongpeng; Tran, Duc; Chen, Zheng Current Opinion in Electrochemistry, Vol. 31 https://doi.org/10.1016/j.coelec.2021.100875	journal	February 2022
Improving the electrochemical activity of LiMnPO4 via Mn-site co-substitution with Fe and Mg Hu, Chenglin; Yi, Huihua; Fang, Haisheng Electrochemistry Communications, Vol. 12, Issue 12 https://doi.org/10.1016/j.elecom.2010.10.024	journal	December 2010
Electrochemical lithiation and delithiation of LiMnPO4: Effect of cation substitution Lee, Jong-Won; Park, Min-Sik; Anass, Benayad Electrochimica Acta, Vol. 55, Issue 13 https://doi.org/10.1016/j.electacta.2010.02.097	journal	May 2010
FTIR spectroscopy of a LiMnPO4 composite cathode Norberg, Nick S.; Kostecki, Robert Electrochimica Acta, Vol. 56, Issue 25 https://doi.org/10.1016/j.electacta.2011.07.116	journal	October 2011
Probing the morphology dependence, size preference and electron/ion conductance of manganese-based lithium transition-metal phosphate as cathode materials for high-performance lithium-ion battery Wang, Yan; Yu, Faquan Journal of Alloys and Compounds, Vol. 850 https://doi.org/10.1016/j.jallcom.2020.156773	journal	January 2021
Current state of high voltage olivine structured LiMPO4 cathode materials for energy storage applications: A review Tolganbek, Nurbol; Yerkinbekova, Yerkezhan; Kalybekkyzy, Sandugash Journal of Alloys and Compounds, Vol. 882 https://doi.org/10.1016/j.jallcom.2021.160774	journal	November 2021
Dramatic improvement in high-rate capability of LiMnPO4 nanosheets via crystallite size regulation Han, Jing; Yang, Jun; Xu, Zhixin Journal of Alloys and Compounds, Vol. 894 https://doi.org/10.1016/j.jallcom.2021.162510	journal	February 2022
Contribution of calcium ion doping to the rate property for LiFe0.5Mn0.5PO4/C Liu, Weifang; Liu, Xichang; Hao, Rui Journal of Electroanalytical Chemistry, Vol. 929 https://doi.org/10.1016/j.jelechem.2022.117117	journal	January 2023
Local structure and redox energies of lithium phosphates with olivine- and Nasicon-like structures Salah, A.; Jozwiak, P.; Garbarczyk, J. Journal of Power Sources, Vol. 140, Issue 2 https://doi.org/10.1016/j.jpowsour.2004.08.029	journal	February 2005
Effect of particle size on LiMnPO4 cathodes Drezen, Thierry; Kwon, Nam-Hee; Bowen, Paul Journal of Power Sources, Vol. 174, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.06.203	journal	December 2007
Substituted transition metal phospho olivines LiMM′PO4 (M = Mn, M′ = Fe, Co, Mg): Optimisation routes for LiMnPO4 Köntje, M.; Memm, M.; Axmann, P. Progress in Solid State Chemistry, Vol. 42, Issue 4 https://doi.org/10.1016/j.progsolidstchem.2014.04.005	journal	December 2014
A review of wind energy technologies Joselin Herbert, G. M.; Iniyan, S.; Sreevalsan, E. Renewable and Sustainable Energy Reviews, Vol. 11, Issue 6 https://doi.org/10.1016/j.rser.2005.08.004	journal	August 2007
Lithium Transport Properties in LiMn _1−α Fe _α PO ₄ Olivine Cathodes Di Lecce, Daniele; Hassoun, Jusef The Journal of Physical Chemistry C, Vol. 119, Issue 36 https://doi.org/10.1021/acs.jpcc.5b06727	journal	August 2015
Graphite-Embedded Lithium Iron Phosphate for High-Power–Energy Cathodes Li, Fan; Tao, Ran; Tan, Xinyi Nano Letters, Vol. 21, Issue 6 https://doi.org/10.1021/acs.nanolett.1c00037	journal	March 2021
Mechanochemically Assisted Synthesis of High-Entropy Layer-Structured Dittmarite Analogues Fan, Juntian; Wang, Tao; Yuan, Yating ACS Applied Energy Materials, Vol. 5, Issue 3 https://doi.org/10.1021/acsaem.1c03869	journal	March 2022
Electrochemical Energy Storage for Green Grid Yang, Zhenguo; Zhang, Jianlu; Kintner-Meyer, Michael C. W. Chemical Reviews, Vol. 111, Issue 5, p. 3577-3613 https://doi.org/10.1021/cr100290v	journal	May 2011
The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
High entropy oxides for reversible energy storage Sarkar, Abhishek; Velasco, Leonardo; Wang, Di Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05774-5	journal	August 2018
Hidden structural and chemical order controls lithium transport in cation-disordered oxides for rechargeable batteries Ji, Huiwen; Urban, Alexander; Kitchaev, Daniil A. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08490-w	journal	February 2019
A reflection on lithium-ion battery cathode chemistry Manthiram, Arumugam Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15355-0	journal	March 2020
Lithium-based polyanion oxide cathodes Manthiram, Arumugam; Goodenough, John B. Nature Energy, Vol. 6, Issue 8 https://doi.org/10.1038/s41560-021-00865-y	journal	August 2021
Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries Lun, Zhengyan; Ouyang, Bin; Kwon, Deok-Hwang Nature Materials, Vol. 20, Issue 2 https://doi.org/10.1038/s41563-020-00816-0	journal	October 2020
Lithium containing layered high entropy oxide structures Wang, Junbo; Cui, Yanyan; Wang, Qingsong Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-75134-1	journal	October 2020
Synthesis, characterization and observation of antisite defects in LiNiPO4 nanomaterials Kempaiah Devaraju, Murukanahally; Duc Truong, Quang; Hyodo, Hiroshi Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep11041	journal	June 2015
Ultrafast nano-spherical single-crystalline LiMn _0.792 Fe _0.198 Mg _0.010 PO ₄ solid-solution confined among unbundled interstices of SGCNTs Kisu, Kazuaki; Iwama, Etsuro; Onishi, Wataru J. Mater. Chem. A, Vol. 2, Issue 48 https://doi.org/10.1039/C4TA04723K	journal	January 2014
Influence of HDI as a cathode film-forming additive on the performance of LiFe_0.2Mn_0.8PO₄/C cathode Xu, Xiaoyue; Qin, Yinping; Yang, Wenchao RSC Advances, Vol. 7, Issue 67 https://doi.org/10.1039/C7RA04979J	journal	January 2017
Multi-anionic and -cationic compounds: new high entropy materials for advanced Li-ion batteries Wang, Qingsong; Sarkar, Abhishek; Wang, Di Energy & Environmental Science, Vol. 12, Issue 8 https://doi.org/10.1039/C9EE00368A	journal	January 2019
Recent progress of high-entropy materials for energy storage and conversion Amiri, Azadeh; Shahbazian-Yassar, Reza Journal of Materials Chemistry A, Vol. 9, Issue 2 https://doi.org/10.1039/D0TA09578H	journal	January 2021
Entropy stabilized cubic Li₇La₃Zr₂O₁₂ with reduced lithium diffusion activation energy: studied using solid-state NMR spectroscopy Fan, Juntian; Wang, Tao; Bridges, Craig A. RSC Advances, Vol. 13, Issue 29 https://doi.org/10.1039/D3RA02206D	journal	January 2023
Recent advances in the research of polyanion-type cathode materials for Li-ion batteries Gong, Zhengliang; Yang, Yong Energy & Environmental Science, Vol. 4, Issue 9 https://doi.org/10.1039/c0ee00713g	journal	January 2011
Synthesis and structure of LiCaPo4 by combined X-ray and neutron powder diffraction Lightfoot, Philip; Pienkowski, Marian C.; Bruce, Peter G. Journal of Materials Chemistry, Vol. 1, Issue 6 https://doi.org/10.1039/jm9910101061	journal	January 1991
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries Padhi, A. K. Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194 https://doi.org/10.1149/1.1837571	journal	April 1997
Communication—Design of LiNi_0.2Mn_0.2Co_0.2Fe_0.2Ti_0.2O₂ as a High-Entropy Cathode for Lithium-Ion Batteries Guided by Machine Learning Sturman, James; Yim, Chae-Ho; Baranova, Elena A. Journal of The Electrochemical Society, Vol. 168, Issue 5 https://doi.org/10.1149/1945-7111/ac00f4	journal	May 2021
A General Discussion of Li Ion Battery Safety Doughty, D. H.; Roth, E. P. Interface magazine, Vol. 21, Issue 2 https://doi.org/10.1149/2.F03122if	journal	January 2012
Improving electrochemical performance of LiCoPO₄via Mn substitution Han, Y. H.; Ni, J. F.; Liu, J. Z. Materials Technology, Vol. 28, Issue 5 https://doi.org/10.1179/1753555713Y.0000000062	journal	September 2013
Nanostructured high-entropy materials Haché, Michel J. R.; Cheng, Changjun; Zou, Yu Journal of Materials Research, Vol. 35, Issue 8 https://doi.org/10.1557/jmr.2020.33	journal	March 2020

Similar Records

Stabilization of Lithium Transition Metal Silicates in the Olivine Structure

Journal Article · 2017 · Inorganic Chemistry · OSTI ID:1393479

Sun, Xiaoqi; Tripathi, Rajesh; Popov, Guerman; +2 more

Manganese-rich high entropy oxides for lithium-ion batteries:materials design approaches to address voltage fade

Journal Article · 2024 · Journal of Materials Chemistry. A · OSTI ID:2460438

Huang, Cynthia; Luo, Jessica; Mansley, Zachary R.; +14 more

Synthesis, crystal structure, and electrode characteristics of LiMnPO{sub 4}(OH) cathode for lithium batteries

Journal Article · 2012 · Journal of Solid State Chemistry · OSTI ID:22012049

Yang, Yang; Hirayama, Masaaki; Yonemura, Masao; +1 more

Related Subjects

25 ENERGY STORAGE
calcination
chemical elements
crystallographic defects
energy storage
entropy
lithium-ion batteries
minerals
phosphates
scanning electron microscopy
x-ray diffraction

Title: Lattice engineering of high-entropy olivine-type lithium metal phosphate as high-voltage cathodes

Citation Formats

References (47)

Similar Records

Related Subjects