Local Structure Distortion and Oxygen Substitution in Zr-Based Halide Nanocomposites: Key to Enhanced Ionic Conductivity for All-Solid-State Batteries
Designing highly conductive and (electro)chemically stable inorganic solid electrolytes (SEs) from cost-effective precursors is critical for developing all-solid-state batteries (ASSBs). Herein, we report a series of low-cost zirconium (Zr) -based halide nanocomposite SEs, Li<sub>1+2<i>x</i></sub>Zr<sub>1-<i>x</i></sub>Ta<sub><i>x</i></sub>O<sub>3<i>x</i></sub>Cl<sub>5-3<i>x</i></sub> (<i>x</i> = 0.33, 0.4, 0.5), synthesized via mechanochemical interaction between LiTaO<sub>3</sub> and ZrCl<sub>4</sub>. The optimized composition, Li<sub>1.8</sub>Zr<sub>0.6</sub>Ta<sub>0.4</sub>O<sub>1.2</sub>Cl<sub>3.8</sub>, exhibits enhanced ionic conductivity from 0.46 to 1.12 mS cm<sup>-1</sup> and decreased electronic conductivity. Mechanochemical processing modulates the local structural environments of the halide nanocomposites, facilitating ion transport. Combined characterization, including X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and synchrotron X-ray absorption spectroscopy, reveals that oxygen-substituted nanocomposites with distorted local structures are key to improving ion transport. Finally, we demonstrate ASSBs using Li<sub>1.8</sub>Zr<sub>0.6</sub>Ta<sub>0.4</sub>O<sub>1.2</sub>Cl<sub>3.8</sub> as the SE, single-crystalline LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> (scNCM811) as the cathode, and Li-In alloy as the anode, achieving stable cycling at room temperature and 1 C rate.
Authors
- Wei Xue (ORCID: https://orcid.org/0000-0002-6574-1809)
- Zhixu Long
- Kentaro Yamamoto (ORCID: https://orcid.org/0000-0002-8739-4246)
- Shufeng Song (ORCID: https://orcid.org/0000-0001-9049-8305)
- Masashi Kotobuki (ORCID: https://orcid.org/0000-0001-7335-3833)
- Yanming Cui (ORCID: https://orcid.org/0009-0000-5579-298X)
- Shengxian Wang (ORCID: https://orcid.org/0000-0002-7094-511X)
- Hao Li (ORCID: https://orcid.org/0000-0003-3870-5981)
- Ning Hu (ORCID: https://orcid.org/0000-0002-6444-8467)
- Hongyang Shan
- Nur Chamidah (ORCID: https://orcid.org/0000-0002-3086-5481)
Institutions
- Ming Chi University of Technology (TW)
- Chang Gung University of Science and Technology (TW)
- Chongqing University (CN)
- Chang Gung University (TW)
- Hebei University of Technology (CN)
- Battery Park (US)
- China Academy of Engineering Physics (CN)
- Institute of Nuclear Physics (UZ)
- Zhejiang Energy Research Institute (CN)
- Centre for Sustainable Energy (GB)
- Zhejiang Energy Group (China) (CN)
- Nara Women's University (JP)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-07-19
- DOI
- https://doi.org/10.1021/acs.inorgchem.5c02770
- Citations
- 3
- Primary Topic
- Advanced Battery Materials and Technologies
- Type
- article
- Field-Weighted Citation Impact
- 2.19
Funders
- National Natural Science Foundation of China
- Chang Gung University
- Natural Science Foundation of Hebei Province
- Chinese Aeronautical Establishment
- National Science and Technology Council