Proton-exchange induced reactivity in layered oxides for lithium-ion batteries
LiNi<sub>x</sub>Co<sub>y</sub>Mn<sub>1-x-y</sub>O<sub>2</sub> (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<sup>+</sup> 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<sup>+</sup> 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<sup>+</sup> 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.
Authors
- Jinxing Chen (ORCID: https://orcid.org/0000-0001-9254-7430)
- Shyue Ping Ong (ORCID: https://orcid.org/0000-0001-5726-2587)
- Minghao Zhang (ORCID: https://orcid.org/0009-0002-8303-3942)
- Fan Yang (ORCID: https://orcid.org/0000-0003-4858-4036)
- Yanbin Shen (ORCID: https://orcid.org/0000-0002-1278-1137)
- Xuefei Weng (ORCID: https://orcid.org/0000-0003-3671-258X)
- Xiaolu Yu (ORCID: https://orcid.org/0000-0002-4288-3484)
- Panpan Xu (ORCID: https://orcid.org/0000-0001-7277-9920)
- Maura C. Appleberry (ORCID: https://orcid.org/0000-0001-9022-681X)
- Hongpeng Gao (ORCID: https://orcid.org/0000-0002-6640-4070)
- Xingyu Guo (ORCID: https://orcid.org/0000-0002-3456-5347)
- Binglei Jiao
- Christopher James Brooks (ORCID: https://orcid.org/0000-0003-1445-2035)
- Ying Shirley Meng (ORCID: https://orcid.org/0000-0001-8936-8845)
- Zheng Chen (ORCID: https://orcid.org/0000-0002-9186-4298)
- Zhenzhen Yang (ORCID: https://orcid.org/0000-0002-1073-3799)
- Jing Gu (ORCID: https://orcid.org/0009-0003-6085-3574)
- Haodong Liu (ORCID: https://orcid.org/0009-0002-8529-3051)
Institutions
- Argonne National Laboratory (US)
- Chinese Academy of Sciences (CN)
- Fudan University (CN)
- San Diego State University (US)
- University of California San Diego (US)
- Soochow University (CN)
- Suzhou Institute of Nano-tech and Nano-bionics (CN)
- Computational Physics (United States) (US)
- Honda (United States) (US)
Publication Details
- Journal
- Nature Communications
- Published
- 2024-11-13
- DOI
- https://doi.org/10.1038/s41467-024-53731-2
- Citations
- 28
- Primary Topic
- Advancements in Battery Materials
- Type
- article
- Field-Weighted Citation Impact
- 5.84
Funders
- U.S. Department of Energy
- Nissan North America
- University of Chicago
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- Government of Jiangsu Province
- Nissan Motor Company
- Natural Science Foundation of Jiangsu Province
- Office of Science
- Office of Energy Efficiency and Renewable Energy
- University of California, San Diego
- Suzhou Institute of Nanotechnology, Chinese Academy of Sciences
- Basic Energy Sciences
- Office of Energy Efficiency
- Argonne National Laboratory
- Oak Ridge National Laboratory