Coordination-Dependent Chemical Reactivity of TFSI Anions at a Mg Metal Interface
Abstract
Charge transfer across the electrode–electrolyte interface is a highly complex and convoluted process involving diverse solvated species with varying structures and compositions. Despite recent advances in in situ and operando interfacial analysis, molecular specific reactivity of solvated species is inaccessible due to a lack of precise control over the interfacial constituents and/or an unclear understanding of their spectroscopic fingerprints. However, such molecular-specific understanding is critical to the rational design of energy-efficient solid–electrolyte interphase layers. We have employed ion soft landing, a versatile and highly controlled method, to prepare well-defined interfaces assembled with selected ions, either as solvated species or as bare ions, with distinguishing molecular precision. Equipped with precise control over interfacial composition, we employed in situ multimodal spectroscopic characterization to unravel the molecular specific reactivity of Mg solvated species comprising (i.e., bis(trifluoromethanesulfonyl)imide, TFSI–) anions and solvent molecules (i.e., dimethoxyethane, DME/G1) on a Mg metal surface relevant to multivalent Mg batteries. In situ multimodal spectroscopic characterization revealed higher reactivity of the undercoordinated solvated species [Mg-TFSI-G1]+ compared to the fully coordinated [Mg-TFSI-(G1)2]+ species or even the bare TFSI–. These results were corroborated by the computed reaction pathways and energy barriers for decomposition of the TFSI– within Mg solvated species relative tomore »
- Authors:
-
[1];
[2];
[2];
[3];
[1];
[4];
[4];
[2];
[1];
[2];
[1]
- Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Environmental Measurements Laboratory (EML), New York, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1958189
- Alternate Identifier(s):
- OSTI ID: 2339564
- Report Number(s):
- PNNL-SA-178429
Journal ID: ISSN 1944-8244
- Grant/Contract Number:
- AC05-76RL01830; AC06-76RLO; AC02-05CH11231; AC02-06CH11357; AC06-76RLO1830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 15; Journal Issue: 5; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; surface reactivity; battery electrolytes; Mg metal; ion soft landing; solid-electrolyte interphase formation
Citation Formats
Prabhakaran, Venkateshkumar, Agarwal, Garvit, Howard, Jason D., Wi, Sungun, Shutthanandan, Vaithiyalingam, Nguyen, Dan-Thien, Soule, Luke, Johnson, Grant E., Liu, Yi-Sheng, Yang, Feipeng, Feng, Xuefei, Guo, Jinghua, Hankins, Kie, Curtiss, Larry A., Mueller, Karl T., Assary, Rajeev S., and Murugesan, Vijayakumar. Coordination-Dependent Chemical Reactivity of TFSI Anions at a Mg Metal Interface. United States: N. p., 2023.
Web. doi:10.1021/acsami.2c18477.
Prabhakaran, Venkateshkumar, Agarwal, Garvit, Howard, Jason D., Wi, Sungun, Shutthanandan, Vaithiyalingam, Nguyen, Dan-Thien, Soule, Luke, Johnson, Grant E., Liu, Yi-Sheng, Yang, Feipeng, Feng, Xuefei, Guo, Jinghua, Hankins, Kie, Curtiss, Larry A., Mueller, Karl T., Assary, Rajeev S., & Murugesan, Vijayakumar. Coordination-Dependent Chemical Reactivity of TFSI Anions at a Mg Metal Interface. United States. https://doi.org/10.1021/acsami.2c18477
Prabhakaran, Venkateshkumar, Agarwal, Garvit, Howard, Jason D., Wi, Sungun, Shutthanandan, Vaithiyalingam, Nguyen, Dan-Thien, Soule, Luke, Johnson, Grant E., Liu, Yi-Sheng, Yang, Feipeng, Feng, Xuefei, Guo, Jinghua, Hankins, Kie, Curtiss, Larry A., Mueller, Karl T., Assary, Rajeev S., and Murugesan, Vijayakumar. Mon .
"Coordination-Dependent Chemical Reactivity of TFSI Anions at a Mg Metal Interface". United States. https://doi.org/10.1021/acsami.2c18477. https://www.osti.gov/servlets/purl/1958189.
@article{osti_1958189,
title = {Coordination-Dependent Chemical Reactivity of TFSI Anions at a Mg Metal Interface},
author = {Prabhakaran, Venkateshkumar and Agarwal, Garvit and Howard, Jason D. and Wi, Sungun and Shutthanandan, Vaithiyalingam and Nguyen, Dan-Thien and Soule, Luke and Johnson, Grant E. and Liu, Yi-Sheng and Yang, Feipeng and Feng, Xuefei and Guo, Jinghua and Hankins, Kie and Curtiss, Larry A. and Mueller, Karl T. and Assary, Rajeev S. and Murugesan, Vijayakumar},
abstractNote = {Charge transfer across the electrode–electrolyte interface is a highly complex and convoluted process involving diverse solvated species with varying structures and compositions. Despite recent advances in in situ and operando interfacial analysis, molecular specific reactivity of solvated species is inaccessible due to a lack of precise control over the interfacial constituents and/or an unclear understanding of their spectroscopic fingerprints. However, such molecular-specific understanding is critical to the rational design of energy-efficient solid–electrolyte interphase layers. We have employed ion soft landing, a versatile and highly controlled method, to prepare well-defined interfaces assembled with selected ions, either as solvated species or as bare ions, with distinguishing molecular precision. Equipped with precise control over interfacial composition, we employed in situ multimodal spectroscopic characterization to unravel the molecular specific reactivity of Mg solvated species comprising (i.e., bis(trifluoromethanesulfonyl)imide, TFSI–) anions and solvent molecules (i.e., dimethoxyethane, DME/G1) on a Mg metal surface relevant to multivalent Mg batteries. In situ multimodal spectroscopic characterization revealed higher reactivity of the undercoordinated solvated species [Mg-TFSI-G1]+ compared to the fully coordinated [Mg-TFSI-(G1)2]+ species or even the bare TFSI–. These results were corroborated by the computed reaction pathways and energy barriers for decomposition of the TFSI– within Mg solvated species relative to bare TFSI–. Finally, we evaluated the TFSI reactivity under electrochemical conditions using Mg(TFSI)2–DME-based phase-separated electrolytes representing different solvated constituents. Based on our multimodal study, we report a detailed understanding of TFSI– decomposition processes as part of coordinated solvated species at a Mg-metal anode that will aid the rational design of improved sustainable electrochemical energy technologies.},
doi = {10.1021/acsami.2c18477},
journal = {ACS Applied Materials and Interfaces},
number = 5,
volume = 15,
place = {United States},
year = {Mon Jan 30 00:00:00 EST 2023},
month = {Mon Jan 30 00:00:00 EST 2023}
}
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Figure 1: Isolating solvated interfacial ions. (a) Schematic diagram of the electrical double layer showing the distribution of TFSI- ions with fully coordinated, under-coordinated, and bare structures near the electrode-electrolyte interface. (b-d) Calculated structures of the bare TFSI-, undercoordinated [MgTFSI-G1]+, and fully coordinated [Mg-TFSI-(G1)2]+ investigated in this study. Note thatmore »
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