Proton-exchange induced reactivity in layered oxides for lithium-ion batteries

Xu, Panpan; Guo, Xingyu; Jiao, Binglei; Chen, Jinxing; Zhang, Minghao; Liu, Haodong; Yu, Xiaolu; Appleberry, Maura; Yang, Zhenzhen; Gao, Hongpeng; Yang, Fan; Weng, Xuefei; Shen, Yanbin; Gu, Jing; Meng, Ying Shirley; Brooks, Christopher; Ong, Shyue Ping; Chen, Zheng

doi:10.1038/s41467-024-53731-2

Title: Proton-exchange induced reactivity in layered oxides for lithium-ion batteries

Journal Article · 12 November 2024 · Nature Communications

DOI: https://doi.org/10.1038/s41467-024-53731-2 · OSTI ID:2477089

Xu, Panpan ^[1];

^[2]; Jiao, Binglei ^[3];

^[4];

^[5]; Liu, Haodong ^[5]; Yu, Xiaolu ^[5];

^[5]; Yang, Zhenzhen ^[6]; Gao, Hongpeng ^[5]; Yang, Fan ^[7];

^[3];

^[3]; Gu, Jing ^[5];

^[5]; Brooks, Christopher ^[8];

^[5];

^[5]

University of California, San Diego, La Jolla, CA (United States); Chinese Academy of Sciences, Suzhou (China)
University of California, San Diego, La Jolla, CA (United States); Fudan University, Shanghai (China)
Chinese Academy of Sciences, Suzhou (China)
Soochow University, Jiangsu (China)
University of California, San Diego, La Jolla, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
San Diego State University, CA (United States)
Honda Research Institute USA, Columbus, OH (United States)

LiNi_xCo_yMn_1-x-yO₂ (0 < x, y < 1, NCM) is the dominant positive material for the state-of-the-art lithium-ion batteries. However, the sensitivity of NCM materials to moisture makes their manufacturing, storage, transportation, electrode processing and recycling complicated. Although it is recognized that protons play a critical role in their structure stability and performance, proton exchange with Li⁺ in NCM materials has not been well understood. Here, we employ advanced characterizations and computational studies to elucidate how protons intercalate into the layered structure of NCM, leading to the leaching of Li⁺ and the formation of protonated NCM. It is found that protonation facilitates cation rearrangement and formation of impurity phases in NCM, significantly deteriorating structural stability. The adverse effects induced by protons become increasingly pronounced with a higher Ni content in NCM. Through a comprehensive investigation into the thermodynamics and kinetics of protonation, we discover that Li deficiencies in NCM materials can be resolved via solution process in the presence of Li⁺ ions and controlled proton concentration. The underlying mechanism of relithiation is further explored through materials characterizations and kinetics modeling. This work provides crucial insights into controlling structural and compositional defects of Li-ion battery positive material in complicated processing environment.

View Journal Article

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2477089

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Springer Science and Business Media LLCCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Combining In Situ Synchrotron X-Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium-Ion Batteries Nam, Kyung-Wan; Bak, Seong-Min; Hu, Enyuan Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201200693	journal	June 2012
Surface Modification Engineering Enabling 4.6 V Single‐Crystalline Ni‐Rich Cathode with Superior Long‐Term Cyclability Fan, Xin‐Ming; Huang, Ying‐De; Wei, Han‐Xin Advanced Functional Materials, Vol. 32, Issue 6 https://doi.org/10.1002/adfm.202109421	journal	October 2021
Higher, Stronger, Better…︁ A Review of 5 Volt Cathode Materials for Advanced Lithium-Ion Batteries Kraytsberg, Alexander; Ein-Eli, Yair Advanced Energy Materials, Vol. 2, Issue 8 https://doi.org/10.1002/aenm.201200068	journal	June 2012
Water Soluble Binder, an Electrochemical Performance Booster for Electrode Materials with High Energy Density Li, Jun-Tao; Wu, Zhan-Yu; Lu, Yan-Qiu Advanced Energy Materials, Vol. 7, Issue 24 https://doi.org/10.1002/aenm.201701185	journal	July 2017
Layered Oxide Cathodes for Sodium-Ion Batteries: Phase Transition, Air Stability, and Performance Wang, Peng-Fei; You, Ya; Yin, Ya-Xia Advanced Energy Materials, Vol. 8, Issue 8 https://doi.org/10.1002/aenm.201701912	journal	November 2017
Modified High-Nickel Cathodes with Stable Surface Chemistry Against Ambient Air for Lithium-Ion Batteries You, Ya; Celio, Hugo; Li, Jianyu Angewandte Chemie International Edition, Vol. 57, Issue 22 https://doi.org/10.1002/anie.201801533	journal	April 2018
The alloy theoretic automated toolkit: A user guide van de Walle, A.; Asta, M.; Ceder, G. Calphad, Vol. 26, Issue 4 https://doi.org/10.1016/S0364-5916(02)80006-2	journal	December 2002
Synthesis, XRD characterization and electrochemical performance of overlithiated LiNiO2 Moshtev, R.; Zlatilova, P.; Vasilev, S. Journal of Power Sources, Vol. 81-82 https://doi.org/10.1016/S0378-7753(99)00247-5	journal	September 1999
Facile and efficient fabrication of Li3PO4-coated Ni-rich cathode for high-performance lithium-ion battery Zou, Pinjuan; Lin, Zhihua; Fan, Mengna Applied Surface Science, Vol. 504 https://doi.org/10.1016/j.apsusc.2019.144506	journal	February 2020
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav Computational Materials Science, Vol. 68 https://doi.org/10.1016/j.commatsci.2012.10.028	journal	February 2013
Electrochemical behavior of LiCoO₂ as aqueous lithium-ion battery electrodes Ruffo, Riccardo; Wessells, Colin; Huggins, Robert A. Electrochemistry Communications, Vol. 11, Issue 2, p. 247-249 https://doi.org/10.1016/j.elecom.2008.11.015	journal	February 2009
The effects of ambient storage conditions on the structural and electrochemical properties of NMC-811 cathodes for Li-ion batteries Busà, Chiara; Belekoukia, Meltiani; Loveridge, Melanie J. Electrochimica Acta, Vol. 366 https://doi.org/10.1016/j.electacta.2020.137358	journal	January 2021
Direct conversion of degraded LiCoO2 cathode materials into high-performance LiCoO2: A closed-loop green recycling strategy for spent lithium-ion batteries Wang, Junxiong; Liang, Zheng; Zhao, Yun Energy Storage Materials, Vol. 45 https://doi.org/10.1016/j.ensm.2021.12.013	journal	March 2022
Efficient Direct Recycling of Lithium-Ion Battery Cathodes by Targeted Healing Xu, Panpan; Dai, Qiang; Gao, Hongpeng Joule, Vol. 4, Issue 12 https://doi.org/10.1016/j.joule.2020.10.008	journal	December 2020
Diagnosis tools for humidity-born surface contaminants on Li[Ni0.8Mn0.1Co0.1]O2 cathode materials for lithium batteries Schuer, Annika R.; Kuenzel, Matthias; Yang, Shuo Journal of Power Sources, Vol. 525 https://doi.org/10.1016/j.jpowsour.2022.231111	journal	March 2022
Protonation of Li (Co,Ni,Mn)O2 compounds in acidic conditions Aleksandrova, Irina; Medina, Elena A.; Karppinen, Maarit Journal of Solid State Chemistry, Vol. 289 https://doi.org/10.1016/j.jssc.2020.121478	journal	September 2020
In-Depth Characterization of Lithium-Metal Surfaces with XPS and ToF-SIMS: Toward Better Understanding of the Passivation Layer Otto, Svenja-K.; Moryson, Yannik; Krauskopf, Thorben Chemistry of Materials, Vol. 33, Issue 3 https://doi.org/10.1021/acs.chemmater.0c03518	journal	January 2021
Influence of Stacking on H⁺ Intercalation in Layered ACoO₂ (A = Li, Na) Cathode Materials and Implications for Aqueous Li-Ion Batteries: A First-Principles Investigation Posada-Pérez, Sergio; Rignanese, Gian-Marco; Hautier, Geoffroy Chemistry of Materials, Vol. 33, Issue 17 https://doi.org/10.1021/acs.chemmater.1c01887	journal	August 2021
Calculations of Oxygen Adsorption-Induced Surface Reconstruction and Oxide Formation on Cu(100) Lian, Xin; Xiao, Penghao; Liu, Renlong Chemistry of Materials, Vol. 29, Issue 4 https://doi.org/10.1021/acs.chemmater.6b02722	journal	February 2017
Towards First Principles-Based Prediction of Highly Accurate Electrochemical Pourbaix Diagrams Zeng, Zhenhua; Chan, Maria K. Y.; Zhao, Zhi-Jian The Journal of Physical Chemistry C, Vol. 119, Issue 32 https://doi.org/10.1021/acs.jpcc.5b03169	journal	July 2015
Electrochemical Properties and Crystal Structure of Li ⁺ /H ⁺ Cation-Exchanged LiNiO ₂ Toma, Takahiro; Maezono, Ryo; Hongo, Kenta ACS Applied Energy Materials, Vol. 3, Issue 4 https://doi.org/10.1021/acsaem.0c00602	journal	April 2020
Bifunctional Surface Coating of LiNbO₃ on High-Ni Layered Cathode Materials for Lithium-Ion Batteries Kim, Jong Hwa; Kim, Hyeongwoo; Choi, Wonchang ACS Applied Materials & Interfaces, Vol. 12, Issue 31 https://doi.org/10.1021/acsami.0c10799	journal	July 2020
Conductive Polymers Encapsulation To Enhance Electrochemical Performance of Ni-Rich Cathode Materials for Li-Ion Batteries Cao, Yanbing; Qi, Xianyue; Hu, Kaihua ACS Applied Materials & Interfaces, Vol. 10, Issue 21 https://doi.org/10.1021/acsami.8b02396	journal	May 2018
Resolving the Compositional and Structural Defects of Degraded LiNi _x Co _y Mn _z O ₂ Particles to Directly Regenerate High-Performance Lithium-Ion Battery Cathodes Shi, Yang; Chen, Gen; Liu, Fang ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b00833	journal	June 2018
Mitigating the Impact of Thermal Binder Removal for Direct Li-Ion Battery Recycling Ross, Bradley J.; LeResche, Michael; Liu, Donghao ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 33 https://doi.org/10.1021/acssuschemeng.0c03424	journal	July 2020
Design and Optimization of the Direct Recycling of Spent Li-Ion Battery Cathode Materials Xu, Panpan; Yang, Zhenzhen; Yu, Xiaolu ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 12 https://doi.org/10.1021/acssuschemeng.0c09017	journal	March 2021
Metallurgy Inspired Formation of Homogeneous Al ₂ O ₃ Coating Layer To Improve the Electrochemical Properties of LiNi _0.8 Co _0.1 Mn _0.1 O ₂ Cathode Material Dong, Mingxia; Wang, Zhixing; Li, Hangkong ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 11 https://doi.org/10.1021/acssuschemeng.7b02178	journal	October 2017
Structural Changes and Thermal Stability of Charged LiNi _x Mn _y Co _z O ₂ Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning ACS Applied Materials & Interfaces, Vol. 6, Issue 24 https://doi.org/10.1021/am506712c	journal	December 2014
Correlation Between Oxygen Vacancy, Microstrain, and Cation Distribution in Lithium-Excess Layered Oxides During the First Electrochemical Cycle Fell, Christopher R.; Qian, Danna; Carroll, Kyler J. Chemistry of Materials, Vol. 25, Issue 9 https://doi.org/10.1021/cm4000119	journal	April 2013
Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
Aqueous Rechargeable Li and Na Ion Batteries Kim, Haegyeom; Hong, Jihyun; Park, Kyu-Young Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500232y	journal	September 2014
CO Oxidation on the Pd(111) Surface Duan, Zhiyao; Henkelman, Graeme ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs5006025	journal	September 2014
Proton-Induced Disproportionation of Jahn–Teller-Active Transition-Metal Ions in Oxides Due to Electronically Driven Lattice Instability Yaghoobnejad Asl, Hooman; Manthiram, Arumugam Journal of the American Chemical Society, Vol. 142, Issue 50 https://doi.org/10.1021/jacs.0c10044	journal	December 2020
Thermodynamics of Phase Selection in MnO ₂ Framework Structures through Alkali Intercalation and Hydration Kitchaev, Daniil A.; Dacek, Stephen T.; Sun, Wenhao Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b11301	journal	February 2017
Collapse of LiNi _{1– x – y} Co _x Mn _y O ₂ Lattice at Deep Charge Irrespective of Nickel Content in Lithium-Ion Batteries Li, Wangda; Asl, Hooman Yaghoobnejad; Xie, Qiang Journal of the American Chemical Society, Vol. 141, Issue 13 https://doi.org/10.1021/jacs.8b13798	journal	March 2019
Enhanced Cyclability for Sulfur Cathode Achieved by a Water-Soluble Binder He, Min; Yuan, Li-Xia; Zhang, Wu-Xing The Journal of Physical Chemistry C, Vol. 115, Issue 31 https://doi.org/10.1021/jp2043416	journal	July 2011
Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte Luo, Jia-Yan; Cui, Wang-Jun; He, Ping Nature Chemistry, Vol. 2, Issue 9 https://doi.org/10.1038/nchem.763	journal	August 2010
Direct observation of the oxygenated species during oxygen reduction on a platinum fuel cell cathode Casalongue, Hernan Sanchez; Kaya, Sarp; Viswanathan, Venkatasubramanian Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3817	journal	December 2013
Environmentally stable interface of layered oxide cathodes for sodium-ion batteries Guo, Shaohua; Li, Qi; Liu, Pan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00157-8	journal	July 2017
Non-equilibrium crystallization pathways of manganese oxides in aqueous solution Sun, Wenhao; Kitchaev, Daniil A.; Kramer, Denis Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08494-6	journal	February 2019
A retrospective on lithium-ion batteries Xie, Jing; Lu, Yi-Chun Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16259-9	journal	May 2020
Unlocking the passivation nature of the cathode–air interfacial reactions in lithium ion batteries Zou, Lianfeng; He, Yang; Liu, Zhenyu Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17050-6	journal	June 2020
Predicting aqueous stability of solid with computed Pourbaix diagram using SCAN functional Wang, Zhenbin; Guo, Xingyu; Montoya, Joseph npj Computational Materials, Vol. 6, Issue 1 https://doi.org/10.1038/s41524-020-00430-3	journal	October 2020
Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping Liu, Qi; Su, Xin; Lei, Dan Nature Energy, Vol. 3, Issue 11 https://doi.org/10.1038/s41560-018-0180-6	journal	June 2018
Layered lithium cobalt oxide cathodes Manthiram, Arumugam; Goodenough, John B. Nature Energy, Vol. 6, Issue 3 https://doi.org/10.1038/s41560-020-00764-8	journal	March 2021
Uncovering the roles of oxygen vacancies in cation migration in lithium excess layered oxides Qian, Danna; Xu, Bo; Chi, Miaofang Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/C4CP01799D	journal	January 2014
Observation of partial reduction of manganese in the lithium rich layered oxides, 0.4Li ₂ MnO ₃ –0.6LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , during the first charge Shim, Hyung Cheoul; Kim, Donghan; Shin, Dongwook Physical Chemistry Chemical Physics, Vol. 19, Issue 2 https://doi.org/10.1039/C6CP07574F	journal	January 2017
Effective regeneration of LiCoO ₂ from spent lithium-ion batteries: a direct approach towards high-performance active particles Shi, Yang; Chen, Gen; Chen, Zheng Green Chemistry, Vol. 20, Issue 4 https://doi.org/10.1039/C7GC02831H	journal	January 2018
Alternative binders for sustainable electrochemical energy storage – the transition to aqueous electrode processing and bio-derived polymers Bresser, Dominic; Buchholz, Daniel; Moretti, Arianna Energy & Environmental Science, Vol. 11, Issue 11 https://doi.org/10.1039/C8EE00640G	journal	January 2018
Interface molecular wires induce electron transfer from COFs to Pt for enhanced photocatalytic H₂ evolution Zhao, Zhengfeng; Chen, Weiqiang; Zhang, Guofeng Journal of Materials Chemistry A, Vol. 11, Issue 47 https://doi.org/10.1039/D3TA06222H	journal	January 2023
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
Transformation of topologically close-packed β-W to body-centered cubic α-W: Comparison of experiments and computations Barmak, Katayun; Liu, Jiaxing; Harlan, Liam The Journal of Chemical Physics, Vol. 147, Issue 15 https://doi.org/10.1063/1.4995261	journal	October 2017
Recycling spent LiNi _1-x-y Mn _x Co _y O ₂ cathodes to bifunctional NiMnCo catalysts for zinc-air batteries Jiao, Miaolun; Zhang, Qi; Ye, Chenliang Proceedings of the National Academy of Sciences, Vol. 119, Issue 20 https://doi.org/10.1073/pnas.2202202119	journal	May 2022
Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides Aydinol, M. K.; Kohan, A. F.; Ceder, G. Physical Review B, Vol. 56, Issue 3 https://doi.org/10.1103/PhysRevB.56.1354	journal	July 1997
Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states Persson, Kristin A.; Waldwick, Bryn; Lazic, Predrag Physical Review B, Vol. 85, Issue 23 https://doi.org/10.1103/PhysRevB.85.235438	journal	June 2012
Strongly Constrained and Appropriately Normed Semilocal Density Functional Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P. Physical Review Letters, Vol. 115, Issue 3 https://doi.org/10.1103/PhysRevLett.115.036402	journal	July 2015
Special quasirandom structures Zunger, Alex; Wei, S.-H.; Ferreira, L. G. Physical Review Letters, Vol. 65, Issue 3, p. 353-356 https://doi.org/10.1103/PhysRevLett.65.353	journal	July 1990
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries Kang, Kisuk; Shirley Meng, Ying; Breger, Julien Science, Vol. 311, Issue 5763, p. 977-980 https://doi.org/10.1126/science.1122152	journal	February 2006
Lithium Diffusion in Layered Li[sub x]CoO[sub 2] Van der Ven, A. Electrochemical and Solid-State Letters, Vol. 3, Issue 7 https://doi.org/10.1149/1.1391130	journal	January 1999
Hybrid Aqueous Energy Storage Cells Using Activated Carbon and Lithium-Ion Intercalated Compounds Wang, Yong-gang; Lou, Jia-yan; Wu, Wen Journal of The Electrochemical Society, Vol. 154, Issue 3 https://doi.org/10.1149/1.2432056	journal	January 2007
Dry Cell Dynamics: The Bobbin Coleman, J. J. Transactions of The Electrochemical Society, Vol. 90, Issue 1 https://doi.org/10.1149/1.3071765	journal	January 1946
Electrochemical Performance of the LiNi[sub 1/3]Co[sub 1/3]Mn[sub 1/3]O[sub 2] in Aqueous Electrolyte Zheng, Jun; Chen, Jia-jia; Jia, Xin Journal of The Electrochemical Society, Vol. 157, Issue 6 https://doi.org/10.1149/1.3374663	journal	January 2010
Study of the Reactions between Ni-Rich Positive Electrode Materials and Aqueous Solutions and their Relation to the Failure of Li-Ion Cells Hamam, Ines; Zhang, Ning; Liu, Aaron Journal of The Electrochemical Society, Vol. 167, Issue 13 https://doi.org/10.1149/1945-7111/abb9cd	journal	September 2020
Surface-stabilization of LMR-NCM by Washing with Aqueous Buffers to Reduce Gassing and Improve Cycle-Life Hartmann, Louis; Ching, Cheuck Hin; Kipfer, Tim Journal of The Electrochemical Society, Vol. 169, Issue 7 https://doi.org/10.1149/1945-7111/ac7ef0	journal	July 2022
Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange Shkrob, Ilya A.; Gilbert, James A.; Phillips, Patrick J. Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.0861707jes	journal	January 2017
Editors' Choice—Washing of Nickel-Rich Cathode Materials for Lithium-Ion Batteries: Towards a Mechanistic Understanding Pritzl, Daniel; Teufl, Tobias; Freiberg, Anna T. S. Journal of The Electrochemical Society, Vol. 166, Issue 16 https://doi.org/10.1149/2.1351915jes	journal	January 2019

Similar Records

Achieving low-temperature hydrothermal relithiation by redox mediation for direct recycling of spent lithium-ion battery cathodes

Journal Article · 2022 · Energy Storage Materials · OSTI ID:1875810

Yu, Xiaolu; Yu, Sicen; Yang, Zhenzhen; +7 more

Probing the Thermal-Driven Structural and Chemical Degradation of Ni-Rich Layered Cathodes by Co/Mn Exchange

Journal Article · 2020 · Journal of the American Chemical Society · OSTI ID:1775103

Liu, Xiang; Xu, Gui-Liang; Yin, Liang; +11 more

Collapse of LiNi_1–x–yCo_xMn_yO₂ Lattice at Deep Charge Irrespective of Nickel Content in Lithium-Ion Batteries

Journal Article · 2019 · Journal of the American Chemical Society · OSTI ID:2217328

Li, Wangda; Asl, Hooman Yaghoobnejad; Xie, Qiang; +1 more

Related Subjects

batteries

Title: Proton-exchange induced reactivity in layered oxides for lithium-ion batteries

Citation Formats

References (67)

Similar Records

Related Subjects