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Title: Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS

Abstract

Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC, which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positivemore » and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.« less

Authors:
 [1];  [2];  [2];  [2];  [2];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [3];  [4];  [5];  [6]; ORCiD logo [1];  [7]; ORCiD logo [1]
  1. BATTELLE (PACIFIC NW LAB)
  2. UNIVERSITY PROGRAMS
  3. Army Research Laboratory
  4. U. S. Army Research Laboratory
  5. VISITORS
  6. Shandong Normal University
  7. CHINESE ACADEMY OF SCIENCES
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1566754
Report Number(s):
PNNL-SA-131962
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Analytical Chemistry
Additional Journal Information:
Journal Volume: 90; Journal Issue: 5
Country of Publication:
United States
Language:
English

Citation Formats

Zhang, Yanyan, Su, Mao, Yu, Xiaofei, Zhou, Yufan, Wang, Jungang, Cao, Ruiguo, Xu, Wu, Wang, Chongmin, Baer, Donald R., Borodin, Oleg, Xu, Kang, Wang, Yanting, Wang, Xue-Lin, Xu, Zhijie, Wang, Fuyi, and Zhu, Zihua. Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS. United States: N. p., 2018. Web. doi:10.1021/acs.analchem.7b04921.
Zhang, Yanyan, Su, Mao, Yu, Xiaofei, Zhou, Yufan, Wang, Jungang, Cao, Ruiguo, Xu, Wu, Wang, Chongmin, Baer, Donald R., Borodin, Oleg, Xu, Kang, Wang, Yanting, Wang, Xue-Lin, Xu, Zhijie, Wang, Fuyi, & Zhu, Zihua. Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS. United States. doi:10.1021/acs.analchem.7b04921.
Zhang, Yanyan, Su, Mao, Yu, Xiaofei, Zhou, Yufan, Wang, Jungang, Cao, Ruiguo, Xu, Wu, Wang, Chongmin, Baer, Donald R., Borodin, Oleg, Xu, Kang, Wang, Yanting, Wang, Xue-Lin, Xu, Zhijie, Wang, Fuyi, and Zhu, Zihua. Tue . "Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS". United States. doi:10.1021/acs.analchem.7b04921.
@article{osti_1566754,
title = {Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS},
author = {Zhang, Yanyan and Su, Mao and Yu, Xiaofei and Zhou, Yufan and Wang, Jungang and Cao, Ruiguo and Xu, Wu and Wang, Chongmin and Baer, Donald R. and Borodin, Oleg and Xu, Kang and Wang, Yanting and Wang, Xue-Lin and Xu, Zhijie and Wang, Fuyi and Zhu, Zihua},
abstractNote = {Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC, which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.},
doi = {10.1021/acs.analchem.7b04921},
journal = {Analytical Chemistry},
number = 5,
volume = 90,
place = {United States},
year = {2018},
month = {3}
}