Earth-abundant Li-ion cathode materials with nanoengineered microstructures
Manganese-based materials have tremendous potential to become the next-generation lithium-ion cathode as they are Earth abundant, low cost and stable. Here we show how the mobility of manganese cations can be used to obtain a unique nanosized microstructure in large-particle-sized cathode materials with enhanced electrochemical properties. By combining atomic-resolution scanning transmission electron microscopy, four-dimensional scanning electron nanodiffraction and in situ X-ray diffraction, we show that when a partially delithiated, high-manganese-content, disordered rocksalt cathode is slightly heated, it forms a nanomosaic of partially ordered spinel domains of 3-7 nm in size, which impinge on each other at antiphase boundaries. The short coherence length of these domains removes the detrimental two-phase lithiation reaction present near 3 V in a regular spinel and turns it into a solid solution. This nanodomain structure enables good rate performance and delivers 200 mAh g<sup>-1</sup> discharge capacity in a (partially) disordered material with an average primary particle size of ∼5 µm. The work not only expands the synthesis strategies available for developing high-performance Earth-abundant manganese-based cathodes but also offers structural insights into the ability to nanoengineer spinel-like phases.
Authors
- Tara Prasad Mishra (ORCID: https://orcid.org/0000-0002-3000-2555)
- Colin Ophus (ORCID: https://orcid.org/0000-0003-2348-8558)
- Yingzhi Sun (ORCID: https://orcid.org/0000-0003-3559-6863)
- Lu Ma (ORCID: https://orcid.org/0000-0001-9646-0738)
- 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)
- Tucker Holstun (ORCID: https://orcid.org/0000-0001-6804-5772)
- Han‐Ming Hau (ORCID: https://orcid.org/0000-0002-0685-2787)
- Shilong Wang (ORCID: https://orcid.org/0009-0004-8504-5802)
- Zijian Cai (ORCID: https://orcid.org/0000-0002-4908-3180)
- Wanli Yang (ORCID: https://orcid.org/0000-0003-0666-8063)
- Gi‐Hyeok Lee (ORCID: https://orcid.org/0000-0003-2516-2586)
- Tzu‐Yang Huang (ORCID: https://orcid.org/0000-0003-0500-9306)
- Yang Ha (ORCID: https://orcid.org/0000-0001-5684-8420)
- John Turner
- Bryan D. McCloskey (ORCID: https://orcid.org/0000-0001-6599-2336)
- Ke Chen (ORCID: https://orcid.org/0000-0003-3511-3112)
- Xiaochen Yang (ORCID: https://orcid.org/0000-0002-8359-5630)
- Karen Bustilo
- Chengyu Song
- Feng Wang (ORCID: https://orcid.org/0000-0003-3036-6735)
Institutions
- Argonne National Laboratory (US)
- Berkeley College (US)
- Lawrence Berkeley National Laboratory (US)
- Brookhaven National Laboratory (US)
- University of California, Berkeley (US)
Publication Details
- Journal
- Nature Nanotechnology
- Published
- 2024-09-19
- DOI
- https://doi.org/10.1038/s41565-024-01787-y
- Citations
- 38
- Primary Topic
- Advancements in Battery Materials
- Type
- article
- Field-Weighted Citation Impact
- 7.93
Funders
- U.S. Department of Energy
- Office of Science
- Office of Energy Efficiency and Renewable Energy
- Basic Energy Sciences
- Office of Energy Efficiency
- Brookhaven National Laboratory