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Electrolyte Reactivity on the MgV2O4 Cathode Surface
Abstract
Predictive understanding of the solvation-dependent reactivity and molecular interaction of electrolyte ions and solvent molecules on reactive electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at electrode-electrolyte interface (EEI) of multivalent Mg batteries. In this work, the isolated intrinsic reactivities of prominent chemical species present in magnesium bis(trifluoromethanesulfonimide) (Mg(TFSI)2) in diglyme (G2) electrolytes, including ionic (TFSI-, [Mg(TFSI)]+, [Mg(TFSI):G2]+, [Mg(TFSI):2G2]+) as well as neutral molecules (G2) on magnesium vanadate cathode (MgV2O4) surface has been studied using a combination of first-principles calculations and multimodal analysis of well-defined cathode electrolyte interphase (CEI) layers. Here, our calculations show that non-solvated [Mg(TFSI)]+ is the strongest adsorbing species on the MgV2O4 surface compared to all other ions while fully solvated [Mg(TFSI):2G2]+ are least favorable to decomposition. The cleavage of C-S bonds in TFSI- to form CF3- is predicted to be most desired pathway for all ionic species, which is followed by the cleavage of C-O bonds of G2 to yield CH3+ or OCH3- species. The strong stabilization and electron transfer between ionic electrolyte species and MgV2O4 is found to significantly favor these decomposition reactions on the surface compared to intrinsic gas phase dissociation. Experimentally, we used state-of-the-artmore »
- Authors:
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[1];
[3];
[4];
[5];
[5];
[2];
[2];
[3];
[2];
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[2];
[1]
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Argonne National Laboratory (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Illinois, Chicago, IL (United States)
- Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
- Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)
- OSTI Identifier:
- 2328492
- Report Number(s):
- PNNL-SA-185103
Journal ID: ISSN 1944-8244
- Grant/Contract Number:
- AC05-76RL01830; AC02-06CH11357; AC02-05CH11231; DMR-2308691; ECCS-1542205; ECCS-2025633; DMR-1720139; DMR-0959470; DMR-1626065
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 15; Journal Issue: 41; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; surface reactivity; ion soft landing; MgV2O4 cathode; Density functional theory; Cathode-electrolyte interphase formation
Citation Formats
Jeong, Heonjae, Nguyen, Dan-Thien, Yang, Yingjie, Buchholz, D. Bruce, Evmenenko, Guennadi, Guo, Jinghua, Yang, Feipeng, Redfern, Paul C., Hu, Jian Zhi, Mueller, Karl T., Klie, Robert, Murugesan, Vijayakumar, Connell, Justin, Prabhakaran, Venkateshkumar, and Cheng, Lei. Electrolyte Reactivity on the MgV2O4 Cathode Surface. United States: N. p., 2023.
Web. doi:10.1021/acsami.3c07875.
Jeong, Heonjae, Nguyen, Dan-Thien, Yang, Yingjie, Buchholz, D. Bruce, Evmenenko, Guennadi, Guo, Jinghua, Yang, Feipeng, Redfern, Paul C., Hu, Jian Zhi, Mueller, Karl T., Klie, Robert, Murugesan, Vijayakumar, Connell, Justin, Prabhakaran, Venkateshkumar, & Cheng, Lei. Electrolyte Reactivity on the MgV2O4 Cathode Surface. United States. https://doi.org/10.1021/acsami.3c07875
Jeong, Heonjae, Nguyen, Dan-Thien, Yang, Yingjie, Buchholz, D. Bruce, Evmenenko, Guennadi, Guo, Jinghua, Yang, Feipeng, Redfern, Paul C., Hu, Jian Zhi, Mueller, Karl T., Klie, Robert, Murugesan, Vijayakumar, Connell, Justin, Prabhakaran, Venkateshkumar, and Cheng, Lei. Sun .
"Electrolyte Reactivity on the MgV2O4 Cathode Surface". United States. https://doi.org/10.1021/acsami.3c07875.
@article{osti_2328492,
title = {Electrolyte Reactivity on the MgV2O4 Cathode Surface},
author = {Jeong, Heonjae and Nguyen, Dan-Thien and Yang, Yingjie and Buchholz, D. Bruce and Evmenenko, Guennadi and Guo, Jinghua and Yang, Feipeng and Redfern, Paul C. and Hu, Jian Zhi and Mueller, Karl T. and Klie, Robert and Murugesan, Vijayakumar and Connell, Justin and Prabhakaran, Venkateshkumar and Cheng, Lei},
abstractNote = {Predictive understanding of the solvation-dependent reactivity and molecular interaction of electrolyte ions and solvent molecules on reactive electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at electrode-electrolyte interface (EEI) of multivalent Mg batteries. In this work, the isolated intrinsic reactivities of prominent chemical species present in magnesium bis(trifluoromethanesulfonimide) (Mg(TFSI)2) in diglyme (G2) electrolytes, including ionic (TFSI-, [Mg(TFSI)]+, [Mg(TFSI):G2]+, [Mg(TFSI):2G2]+) as well as neutral molecules (G2) on magnesium vanadate cathode (MgV2O4) surface has been studied using a combination of first-principles calculations and multimodal analysis of well-defined cathode electrolyte interphase (CEI) layers. Here, our calculations show that non-solvated [Mg(TFSI)]+ is the strongest adsorbing species on the MgV2O4 surface compared to all other ions while fully solvated [Mg(TFSI):2G2]+ are least favorable to decomposition. The cleavage of C-S bonds in TFSI- to form CF3- is predicted to be most desired pathway for all ionic species, which is followed by the cleavage of C-O bonds of G2 to yield CH3+ or OCH3- species. The strong stabilization and electron transfer between ionic electrolyte species and MgV2O4 is found to significantly favor these decomposition reactions on the surface compared to intrinsic gas phase dissociation. Experimentally, we used state-of-the-art ion soft landing to selectively deposit mass-selected TFSI-, [Mg(TFSI):G2]+ and [Mg(TFSI):2G2]+ on MgV2O4 thin film to form well-defined electrolyte-MgV2O4 interface. Analysis of soft-landed interphase using X-ray photoelectron, X-ray absorption near edge structure, electron energy-loss spectroscopies as well as transmission electron microscopy confirmed the presence of decomposition species (e.g., MgFx, carbonates) formed in the interfacial region and the higher amount of MgFx with [Mg(TFSI):G2]+, which corroborates the theoretical observation. Overall, we established the mechanistic pathway for the electrolyte-induced formation of passivating fluorides on MgV2O4 cathode facilitated by the surface adsorption and charge transfer, which provided essential knowledge for rational design of stable electrolytes for multivalent cathodes.},
doi = {10.1021/acsami.3c07875},
journal = {ACS Applied Materials and Interfaces},
number = 41,
volume = 15,
place = {United States},
year = {Sun Oct 08 00:00:00 EDT 2023},
month = {Sun Oct 08 00:00:00 EDT 2023}
}
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