Atomistic Conversion Reaction Mechanism of WO 3 in Secondary Ion Batteries of Li, Na, and Ca
- Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh PA 15261 USA
- Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99352 USA
- School of Physical Electronics, University of Electronic Science and Technology of China, Chengdu 610054 China
- Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA
- Department of Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor MI 48109 USA
Reversible insertion and extraction of ionic species into a host lattice governs the basic operating principle for both rechargeable battery (such as lithium batteries) and electrochromic devices (such as ANA Boeing 787-8 Dreamliner electrochromic window). Intercalation and/or conversion are two fundamental chemical processes for some materials in response to the ion insertion. The interplay between these two chemical processes has never been established. It is speculated that the conversion reaction is initiated by ion intercalation. However, experimental evidence of intercalation and subsequent conversion remains unexplored. Here, using in situ HRTEM and spectroscopy, we captured the atomistic conversion reaction processes during lithium, sodium and calcium ion insertion into tungsten trioxide (WO3) single crystal model electrodes. An intercalation step right prior to conversion is explicitly revealed at atomic scale for the first time for these three ion species. Combining nanoscale diffraction and ab initio molecular dynamics simulations, it is found that, beyond intercalation, the inserted ion-oxygen bonding formation destabilized the transition-metal framework which gradually shrunk, distorted and finally collapsed to a pseudo-amorphous structure. This study provides a full atomistic picture on the transition from intercalation to conversion, which is of essential for material applications in both secondary ion batteries and electrochromic devices.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1327104
- Report Number(s):
- PNNL-SA-114899; 48379; KP1704020
- Journal Information:
- Angewandte Chemie (International Edition), Vol. 55, Issue 21; ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
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