TY - JOUR
T1 - Correlation between Electrolyte Chemistry and Solid Electrolyte Interphase for Reversible Ca Metal Anodes
AU - Hou, Zhen
AU - Zhou, Rui
AU - Yao, Yunduo
AU - Min, Zhiwen
AU - Lu, Ziheng
AU - Zhu, Ye
AU - Tarascon, Jean Marie
AU - Zhang, Biao
N1 - Funding Information:
This work was supported by the General Research Fund (GRF) scheme of the Hong Kong Research Grants Council (Project No. 15306422) and the Hong Kong Polytechnic University (ZE2F). We gratefully acknowledge the support of the University Research Facility on Chemical and Environmental Analysis (UCEA) of PolyU. Z.H. is grateful to Dr. Y. Gao and Ms. D. Wang for assistance in AFM test. Y.Z. acknowledges the financial support from the Research Grants Council of Hong Kong (Project No. C5029‐18E). Z.L. thanks the Bin Shao and Tie‐Yan Liu from Microsoft Research for the help in computational resources.
Funding Information:
This work was supported by the General Research Fund (GRF) scheme of the Hong Kong Research Grants Council (Project No. 15306422) and the Hong Kong Polytechnic University (ZE2F). We gratefully acknowledge the support of the University Research Facility on Chemical and Environmental Analysis (UCEA) of PolyU. Z.H. is grateful to Dr. Y. Gao and Ms. D. Wang for assistance in AFM test. Y.Z. acknowledges the financial support from the Research Grants Council of Hong Kong (Project No. C5029-18E). Z.L. thanks the Bin Shao and Tie-Yan Liu from Microsoft Research for the help in computational resources.
Publisher Copyright:
© 2022 Wiley-VCH GmbH.
PY - 2022/10/19
Y1 - 2022/10/19
N2 - The development of rechargeable Ca metal batteries (RCMBs) is hindered by the Ca2+ passivating solid electrolyte interphases (SEIs). The cation solvation structure dictated by electrolyte chemistry plays a critical role in the SEIs properties. While a relatively weak cation-solvent binding is preferred in Li metal anodes to promote anion-derived SEIs, we demonstrate an enhanced Ca deposition/stripping reversibility under a strong cation-solvent interaction, which is materialized in strongly-solvating solvent and highly-dissociated salt combinations. Such electrolyte formulations benefit the formation of solvent-occupied solvation structure and minimize the anion reduction, resulting in organic-rich/CaF2-poor SEIs for reversible Ca metal anodes. Furthermore, RCMBs paired with an organic cathode using the optimized electrolytes are demonstrated as a proof-of-concept. Our work reveals the paradigm shift in SEIs design for Ca metal anodes, opening up new opportunities for emerging RCMBs.
AB - The development of rechargeable Ca metal batteries (RCMBs) is hindered by the Ca2+ passivating solid electrolyte interphases (SEIs). The cation solvation structure dictated by electrolyte chemistry plays a critical role in the SEIs properties. While a relatively weak cation-solvent binding is preferred in Li metal anodes to promote anion-derived SEIs, we demonstrate an enhanced Ca deposition/stripping reversibility under a strong cation-solvent interaction, which is materialized in strongly-solvating solvent and highly-dissociated salt combinations. Such electrolyte formulations benefit the formation of solvent-occupied solvation structure and minimize the anion reduction, resulting in organic-rich/CaF2-poor SEIs for reversible Ca metal anodes. Furthermore, RCMBs paired with an organic cathode using the optimized electrolytes are demonstrated as a proof-of-concept. Our work reveals the paradigm shift in SEIs design for Ca metal anodes, opening up new opportunities for emerging RCMBs.
KW - Ca Deposition/Stripping
KW - Electrolyte Formulation
KW - Solid Electrolyte Interphase
KW - Solvation Structure
UR - https://www.scopus.com/pages/publications/85143217094
U2 - 10.1002/anie.202214796
DO - 10.1002/anie.202214796
M3 - Journal article
C2 - 36259391
AN - SCOPUS:85143217094
SN - 1433-7851
VL - 61
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 50
M1 - e202214796
ER -