Coherent‐Precipitation‐Stabilized Phase Formation in Over‐Stoichiometric Rocksalt‐Type Li Superionic Conductors
Rationalizing synthetic pathways is crucial for material design and property optimization, especially for polymorphic and metastable phases. Over-stoichiometric rocksalt (ORX) compounds, characterized by their face-sharing configurations, are a promising group of materials with unique properties; however, their development is significantly hindered by challenges in synthesizability. Here, taking the recently identified Li superionic conductor, over-stoichiometric rocksalt Li-In-Sn-O (o-LISO) material as a prototypical ORX compound, the mechanisms of phase formation are systematically investigated. It is revealed that the spinel-like phase with unconventional stoichiometry forms as coherent precipitate from the high-temperature-stabilized cation-disordered rocksalt phase upon fast cooling. This process prevents direct phase decomposition and kinetically locks the system in a metastable state with the desired face-sharing Li configurations. This insight enables us to enhance the ionic conductivity of o-LISO to be >1 mS cm<sup>-1</sup> at room temperature through low-temperature post-annealing. This work offers insights into the synthesis of ORX materials and highlights important opportunities in this new class of materials.
Authors
- Jianming Bai (ORCID: https://orcid.org/0000-0002-0575-2987)
- Gerbrand Ceder (ORCID: https://orcid.org/0000-0001-9275-3605)
- Xinye Zhao (ORCID: https://orcid.org/0000-0001-9139-0638)
- Nathan J. Szymanski (ORCID: https://orcid.org/0000-0003-2255-9676)
- Huiwen Ji (ORCID: https://orcid.org/0000-0001-8091-9428)
- Feng Wang (ORCID: https://orcid.org/0000-0003-4068-9212)
- Zhengyan Lun (ORCID: https://orcid.org/0000-0002-0186-6864)
- Raynald Giovine (ORCID: https://orcid.org/0000-0002-7208-6929)
- Krishna Prasad Koirala (ORCID: https://orcid.org/0000-0002-9137-917X)
- Shilong Wang (ORCID: https://orcid.org/0009-0004-8504-5802)
- Bin Ouyang (ORCID: https://orcid.org/0000-0002-8181-6815)
- Ke Chen (ORCID: https://orcid.org/0000-0003-3511-3112)
- Yu Chen (ORCID: https://orcid.org/0000-0002-5420-7571)
- Chongmin Wang (ORCID: https://orcid.org/0000-0003-3327-0958)
- Xiaochen Yang (ORCID: https://orcid.org/0000-0002-8359-5630)
- Shuoyan Xiong
Institutions
- Florida State University (US)
- Argonne National Laboratory (US)
- Pacific Northwest National Laboratory (US)
- Lawrence Berkeley National Laboratory (US)
- Brookhaven National Laboratory (US)
- University of Utah (US)
- Environmental Molecular Sciences Laboratory (US)
- University of Chinese Academy of Sciences (CN)
- University of California, Berkeley (US)
Publication Details
- Journal
- Advanced Materials
- Published
- 2024-12-23
- DOI
- https://doi.org/10.1002/adma.202416342
- Citations
- 8
- Primary Topic
- Advanced Battery Materials and Technologies
- Type
- article
- Field-Weighted Citation Impact
- 1.67
Funders
- National Science Foundation
- U.S. Department of Energy
- U.S. Department of Commerce
- Battelle
- Washington State University
- National Energy Research Scientific Computing Center
- Office of Science
- Office of Energy Efficiency and Renewable Energy
- Basic Energy Sciences
- Biological and Environmental Research
- Vehicle Technologies Office
- Office of Energy Efficiency
- Argonne National Laboratory
- Brookhaven National Laboratory
- Lawrence Berkeley National Laboratory
- Pacific Northwest National Laboratory