Manipulating the diffusion energy barrier at the lithium metal electrolyte interface for dendrite-free long-life batteries

Creators: Pokharel, Jyotshna; Cresce, Arthur; Pant, Bharat; Yang, Moon Young; Gurung, Ashim; He, Wei; Baniya, Abiral; Lamsal, Buddhi Sagar; Yang, Zhongjiu; Gent, Stephen; Xian, Xiaojun; Cao, Ye; Goddard, William A., III¹; Xu, Kang; Zhou, Yue

1. California Institute of Technology

Abstract

Constructing an artificial solid electrolyte interphase (SEI) on lithium metal electrodes is a promising approach to address the rampant growth of dangerous lithium morphologies (dendritic and dead Li⁰) and low Coulombic efficiency that plague development of lithium metal batteries, but how Li⁺ transport behavior in the SEI is coupled with mechanical properties remains unknown. We demonstrate here a facile and scalable solution-processed approach to form a Li₃N-rich SEI with a phase-pure crystalline structure that minimizes the diffusion energy barrier of Li⁺ across the SEI. Compared with a polycrystalline Li₃N SEI obtained from conventional practice, the phase-pure/single crystalline Li₃N-rich SEI constitutes an interphase of high mechanical strength and low Li⁺ diffusion barrier. We elucidate the correlation among Li⁺ transference number, diffusion behavior, concentration gradient, and the stability of the lithium metal electrode by integrating phase field simulations with experiments. We demonstrate improved reversibility and charge/discharge cycling behaviors for both symmetric cells and full lithium-metal batteries constructed with this Li₃N-rich SEI. These studies may cast new insight into the design and engineering of an ideal artificial SEI for stable and high-performance lithium metal batteries.

Copyright and License

© The Author(s) 2024. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Acknowledgement

This work is supported by the National Science Foundation under awards CBET-2312247, CBET-2038083, and OIA-2132021. A.C. and K.X. thank the support from Joint Center of Energy Storage Research, an Energy Hub funded by US Department of Energy Basic Energy Science. We also acknowledge the part support from NSF ECCS- 2240507 and Department of Defense Batteries and Energy to Advance Commercialization and National Security (BEACONS) center.

Contributions

J.P. and A.G. designed the experiments. A.C. performed XPS characterization. B.P. and Y.C. performed phase field simulation and analysis. W. H., A.B., Z.Y. and B.S.L. assisted in material characterization and participated in performing ex situ SEM experiments. M.Y.Y. conducted DFT calculations. S.G. reviewed the paper. X.X., Y.C., W.A.G., K.X. and Y.Z. analyzed the overall results and supervised the work. J.P. wrote the paper with assistance from coauthors. All authors have discussed the paper.

Data Availability

The authors declare that all the relevant data are available within the paper and its Supplementary Information file or from the corresponding authors upon request.

Conflict of Interest

The authors declare no competing interests.

Files

s41467-024-47521-z.pdf

Files (7.3 MB)

Name	Size	Download all
s41467-024-47521-z.pdf md5:492313246022b112a1251a43a02361e7	3.0 MB	Preview Download
41467_2024_47521_MOESM1_ESM.pdf md5:d22bae1fc2b899ea5a1a64b667aed9b9	4.3 MB	Preview Download

	All versions	This version
Views	0	0
Downloads	0	0
Data volume	0 Bytes	0 Bytes