Li et al. Energy Mater 2021;1:100017 DOI: 10.20517/energymater.2021.21 Energy Materials © The Author(s) 2021. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, sharing, adaptation, distribution and reproduction in any medium or format, for any purpose, even commercially, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. www.energymaterj.com Open Access Review Modulating the lithiophilicity at electrode/electrolyte interface for high-energy Li-metal batteries Cai-Cai Li 1,2,# , Xu-Sheng Zhang 1,2,# , Yu-Hui Zhu 2,# , Ying Zhang 1 , Sen Xin 1,2 , Li-Jun Wan 1,2 , Yu-Guo Guo 1,2 1 CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, China. 2 University of Chinese Academy of Sciences, Beijing 100049, China. # Authors contributed equally. Correspondence to: Dr. Ying Zhang, CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences (CAS), No. 2 of Zhongguancun North First Street, Haidian District, Beijing 100190, China. E-mail: yzhang@iccas.ac.cn; Prof. Sen Xin, CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences (CAS), No. 2 of Zhongguancun North First Street, Haidian District, Beijing 100190, China; University of Chinese Academy of Sciences, No.19 (A) of Yuquan Road, Shijingshan District, Beijing 100049, China. E-mail: xinsen08@iccas.ac.cn How to cite this article: Li CC, Zhang XS, Zhu YH, Zhang Y, Xin S, Wan LJ, Guo YG. Modulating the lithiophilicity at electrode/electrolyte interface for high-energy Li-metal batteries. Energy Mater 2021;1:100017. https://dx.doi.org/10.20517/energymater.2021.21 Received: 3 Nov 2021 First Decision: 17 Nov 2021 Revised: 9 Dec 2021 Accepted: 14 Dec 2021 Published: 31 Dec 2021 Academic Editors: Yuping Wu, Wei Tang Copy Editor: Xi-Jun Chen Production Editor: Xi-Jun Chen Abstract Lithium-metal anodes show significant promise for the construction of high-energy rechargeable batteries due to their high theoretical capacity (3860 mAh g -1 ) and low redox potential (-3.04 V vs. a standard hydrogen electrode). When Li metal is used with conventional liquid and solid electrolytes, the poor lithiophilicity of the electrolyte results in an unfavorable parasitic reaction and uneven distribution of Li + flux at the electrode/electrolyte interface. These issues result in limited cycle life and dendrite problems associated with the Li-metal anode that can lead to rapid performance fade, failure and even safety risks of the battery. The lithiophilicity at the anode/electrolyte interface is important for the stable and safe operation of rechargeable Li-metal batteries. In this review, several factors that affect the lithiophilicity of electrolytes are discussed, including surface energy, roughness and chemical interactions. The existing problems and the strategies for improving the lithiophilicity of different electrolytes are also discussed. This review helps to shed light on the understanding of interfacial chemistry vs. Li metal of various electrolytes and guide interfacial engineering towards the practical realization of high-energy