Identifying Hidden Li‐Si‐O Phases for Lithium‐Ion Batteries via First‐Principles Thermodynamic Calculations

Identifying Hidden Li‐Si‐O Phases for Lithium‐Ion Batteries via First‐Principles Thermodynamic Calculations

Energy & Environmental Materials

10.1002/eem2.12329

http://dx.doi.org/10.1002/eem2.12329

Jiale Qu, Chao Ning, Xiang Feng, Bonan Yao, Bo Liu, Ziheng Lu, Tianshuai Wang, Zhiwei Seh, Siqi Shi, Qianfan Zhang

General Materials Science, Sustainability and the Environment, Waste Management and Disposal, Energy (miscellaneous), Environmental Science (miscellaneous), Water Science and Technology, renewable energy

07 December 2021

Qu, J., Ning, C., Feng, X., Yao, B., Liu, B., Lu, Z., Wang, T., Seh, Z., Shi, S., & Zhang, Q. (2021). Identifying Hidden Li‐Si‐O Phases for Lithium‐Ion Batteries via First‐Principles Thermodynamic Calculations. Energy & Environmental Materials. Portico. https://doi.org/10.1002/eem2.12329

Si-O based materials are promising alloying and conversion-type anode materials for lithium-ion batteries and are recently found to be excellent dendrite-proof layers for lithium-metal batteries. However, only a small fraction of the Li-Si-O compositional space has been reported, significantly impeding the understanding of the phase transition mechanisms and the rational design of these materials both as anodes and as protection layers for lithium-metal anodes. Herein, we identify three new thermodynamically stable phases within the Li-Si-O ternary system (Li2SiO5, Li4SiO6 and Li4SiO8) in addition to the existing records via first-principles calculations. The electronic structure simulation shows that Li2SiO5 and Li4SiO8 phases are metallic in nature, ensuring high electronic conductivity required as electrodes. Moduli calculations demonstrate that the mechanical strength of Li-Si-O phases is much higher than that of lithium metal. The diffusion barriers of interstitial Li range from 0.1 to 0.6 eV and the interstitial Li hopping serves as the dominating diffusion mechanism in the Li-Si-O ternary systems compared with vacancy diffusion. These findings provide a new strategy for future discovery of improved alloying anodes for lithium-ion batteries and offer important insight towards the understanding of the phase transformation mechanism of alloy-type protection layers on lithium metal anodes.

Publisher Copyright

This research / project is supported by the Singapore National Research Foundation - NRF Fellowship
Grant Reference no. : NRF-NRFF2017-04

Overseas Funding:- 1) Beijing Natural Science Foundation (2192029) 2) National Key Research and Development Program of China (2017YFB0702100) 3) National Natural Science Foundation of China (11404017, 12004145) 4) Technology Foundation for Selected Overseas Chinese Scholars 5) Ministry of Human Resources and Social Security of China 6) Academic Excellence Foundation of BUAA for PhD Students. 7) Faraday Institution (grant number FIRG017).

This is the peer reviewed version of the following article: Qu, J., Ning, C., Feng, X., Yao, B., Liu, B., Lu, Z., Wang, T., Seh, Z., Shi, S., &; Zhang, Q. (2021). Identifying Hidden Li‐Si‐O Phases for Lithium‐Ion Batteries via First‐Principles Thermodynamic Calculations. Energy & Environmental Materials. Portico. https://doi.org/10.1002/eem2.12329], which has been published in final form at https://doi.org/10.1002/eem2.12329. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited

https://oar.a-star.edu.sg/communities-collections/articles/18255

2575-0356

Institute of Materials Research and Engineering