Electrolyte Reactivity on the MgV2O4 Cathode Surface

Heonjae Jeong; Dan Thien Nguyen; Yingjie Yang; D. Bruce Buchholz; Guennadi Evmenenko; Jinghua Guo; Feipeng Yang; Paul C. Redfern; Jian Zhi Hu; Karl T. Mueller; Robert Klie; Vijayakumar Murugesan; Justin Connell; Venkateshkumar Prabhakaran; Lei Cheng

doi:10.1021/acsami.3c07875

Electrolyte Reactivity on the MgV₂O₄ Cathode Surface

Heonjae Jeong, Dan Thien Nguyen, Yingjie Yang, D. Bruce Buchholz, Guennadi Evmenenko, Jinghua Guo, Feipeng Yang, Paul C. Redfern, Jian Zhi Hu, Karl T. Mueller, Robert Klie, Vijayakumar Murugesan, Justin Connell, Venkateshkumar Prabhakaran, Lei Cheng

Energy Storage & Conversion

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Predictive understanding of the molecular interaction of electrolyte ions and solvent molecules and their chemical reactivity on electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at the electrode-electrolyte interface of multivalent magnesium 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]⁺, and [Mg(TFSI):2G2]⁺) as well as neutral molecules (G2) on a well-defined magnesium vanadate cathode (MgV₂O₄) surface, have been studied using a combination of first-principles calculations and multimodal spectroscopy analysis. Our calculations show that nonsolvated [Mg(TFSI)]⁺ is the strongest adsorbing species on the MgV₂O₄ surface compared with all other ions while partially solvated [Mg(TFSI):G2]⁺ is the most reactive species. The cleavage of C-S bonds in TFSI^- to form CF₃^- is predicted to be the 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 with 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 a MgV₂O₄ thin film to form a well-defined electrolyte-MgV₂O₄ interface. Analysis of the soft-landed interface 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., MgF_x, carbonates) and the higher amount of MgF_x with [Mg(TFSI):G2]⁺ formed in the interfacial region, which corroborates the theoretical observation. Overall, these results indicate that Mg²⁺ desolvation results in electrolyte decomposition facilitated by surface adsorption, charge transfer, and the formation of passivating fluorides on the MgV₂O₄ cathode surface. This work provides the first evidence of the primary mechanisms leading to electrolyte decomposition at high-voltage oxide surfaces in multivalent batteries and suggests that the design of new, anodically stable electrolytes must target systems that facilitate cation desolvation.

Original language	English
Pages (from-to)	48072-48084
Number of pages	13
Journal	ACS Applied Materials and Interfaces
Volume	15
Issue number	41
DOIs	https://doi.org/10.1021/acsami.3c07875
State	Published - Oct 18 2023

Funding

This research was supported by the Joint Center for Energy Storage Research (JCESR), a U.S. Department of Energy, Energy Innovation Hub. Part of the submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (Argonne). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under contract no. DE-AC02-06CH11357. We gratefully acknowledge the use of the Bebop or Swing or Blues cluster in the Laboratory Computing Resource Center at Argonne National Laboratory. A part of XPS measurements in this work was performed using EMSL, a National Scientific User Facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle Memorial Institute under contract no. DE-AC06-76RLO 1830. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. The preparation and surface characterization of MgVO substrate in this work made use of the Jerome B. Cohen X-Ray Diffraction Facility and the Pulsed Laser Deposition Facility supported by the MRSEC program of the National Science Foundation (DMR-2308691) at the Materials Research Center of Northwestern University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205). The sample preparation work with FIB made use of the Electron Probe Instrumentation Center (EPIC) facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). The acquisition and upgrade of the UIC JEOL JEM ARM200CF was supported by an MRI-R grant (DMR-0959470) and an MRI-grant (DMR-1626065) from NSF. Sample polishing with NanoMill, electron microscopy imaging, and spectroscopy made use of instruments in the Electron Microscopy Core of UIC’s Research Resources Center. 2 4 This research was supported by the Joint Center for Energy Storage Research (JCESR), a U.S. Department of Energy, Energy Innovation Hub. Part of the submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (Argonne). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under contract no. DE-AC02-06CH11357. We gratefully acknowledge the use of the Bebop or Swing or Blues cluster in the Laboratory Computing Resource Center at Argonne National Laboratory. A part of XPS measurements in this work was performed using EMSL, a National Scientific User Facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle Memorial Institute under contract no. DE-AC06-76RLO 1830. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. The preparation and surface characterization of MgV2O4 substrate in this work made use of the Jerome B. Cohen X-Ray Diffraction Facility and the Pulsed Laser Deposition Facility supported by the MRSEC program of the National Science Foundation (DMR-2308691) at the Materials Research Center of Northwestern University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205). The sample preparation work with FIB made use of the Electron Probe Instrumentation Center (EPIC) facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). The acquisition and upgrade of the UIC JEOL JEM ARM200CF was supported by an MRI-R grant (DMR-0959470) and an MRI-grant (DMR-1626065) from NSF. Sample polishing with NanoMill, electron microscopy imaging, and spectroscopy made use of instruments in the Electron Microscopy Core of UIC’s Research Resources Center.

Keywords

Cathode-electrolyte interphase formation
Density functional theory
MgVO cathode
ion soft landing
surface reactivity

Access to Document

10.1021/acsami.3c07875

Cite this

@article{b218585cfba246858a7073483f531560,

title = "Electrolyte Reactivity on the MgV2O4 Cathode Surface",

abstract = "Predictive understanding of the molecular interaction of electrolyte ions and solvent molecules and their chemical reactivity on electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at the electrode-electrolyte interface of multivalent magnesium 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]+, and [Mg(TFSI):2G2]+) as well as neutral molecules (G2) on a well-defined magnesium vanadate cathode (MgV2O4) surface, have been studied using a combination of first-principles calculations and multimodal spectroscopy analysis. Our calculations show that nonsolvated [Mg(TFSI)]+ is the strongest adsorbing species on the MgV2O4 surface compared with all other ions while partially solvated [Mg(TFSI):G2]+ is the most reactive species. The cleavage of C-S bonds in TFSI- to form CF3- is predicted to be the 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 with 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 a MgV2O4 thin film to form a well-defined electrolyte-MgV2O4 interface. Analysis of the soft-landed interface 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) and the higher amount of MgFx with [Mg(TFSI):G2]+ formed in the interfacial region, which corroborates the theoretical observation. Overall, these results indicate that Mg2+ desolvation results in electrolyte decomposition facilitated by surface adsorption, charge transfer, and the formation of passivating fluorides on the MgV2O4 cathode surface. This work provides the first evidence of the primary mechanisms leading to electrolyte decomposition at high-voltage oxide surfaces in multivalent batteries and suggests that the design of new, anodically stable electrolytes must target systems that facilitate cation desolvation.",

keywords = "Cathode-electrolyte interphase formation, Density functional theory, MgVO cathode, ion soft landing, surface reactivity",

author = "Heonjae Jeong and Nguyen, {Dan Thien} and Yingjie Yang and Buchholz, {D. Bruce} and Guennadi Evmenenko and Jinghua Guo and Feipeng Yang and Redfern, {Paul C.} and Hu, {Jian Zhi} and Mueller, {Karl T.} and Robert Klie and Vijayakumar Murugesan and Justin Connell and Venkateshkumar Prabhakaran and Lei Cheng",

note = "Publisher Copyright: {\textcopyright} 2023 UChicago Argonne, LLC. Published by American Chemical Society",

year = "2023",

month = oct,

day = "18",

doi = "10.1021/acsami.3c07875",

language = "English",

volume = "15",

pages = "48072--48084",

journal = "ACS Applied Materials and Interfaces",

issn = "1944-8244",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Electrolyte Reactivity on the MgV2O4 Cathode Surface

AU - Jeong, Heonjae

AU - Nguyen, Dan Thien

AU - Yang, Yingjie

AU - Buchholz, D. Bruce

AU - Evmenenko, Guennadi

AU - Guo, Jinghua

AU - Yang, Feipeng

AU - Redfern, Paul C.

AU - Hu, Jian Zhi

AU - Mueller, Karl T.

AU - Klie, Robert

AU - Murugesan, Vijayakumar

AU - Connell, Justin

AU - Prabhakaran, Venkateshkumar

AU - Cheng, Lei

PY - 2023/10/18

Y1 - 2023/10/18

N2 - Predictive understanding of the molecular interaction of electrolyte ions and solvent molecules and their chemical reactivity on electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at the electrode-electrolyte interface of multivalent magnesium 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]+, and [Mg(TFSI):2G2]+) as well as neutral molecules (G2) on a well-defined magnesium vanadate cathode (MgV2O4) surface, have been studied using a combination of first-principles calculations and multimodal spectroscopy analysis. Our calculations show that nonsolvated [Mg(TFSI)]+ is the strongest adsorbing species on the MgV2O4 surface compared with all other ions while partially solvated [Mg(TFSI):G2]+ is the most reactive species. The cleavage of C-S bonds in TFSI- to form CF3- is predicted to be the 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 with 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 a MgV2O4 thin film to form a well-defined electrolyte-MgV2O4 interface. Analysis of the soft-landed interface 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) and the higher amount of MgFx with [Mg(TFSI):G2]+ formed in the interfacial region, which corroborates the theoretical observation. Overall, these results indicate that Mg2+ desolvation results in electrolyte decomposition facilitated by surface adsorption, charge transfer, and the formation of passivating fluorides on the MgV2O4 cathode surface. This work provides the first evidence of the primary mechanisms leading to electrolyte decomposition at high-voltage oxide surfaces in multivalent batteries and suggests that the design of new, anodically stable electrolytes must target systems that facilitate cation desolvation.

AB - Predictive understanding of the molecular interaction of electrolyte ions and solvent molecules and their chemical reactivity on electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at the electrode-electrolyte interface of multivalent magnesium 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]+, and [Mg(TFSI):2G2]+) as well as neutral molecules (G2) on a well-defined magnesium vanadate cathode (MgV2O4) surface, have been studied using a combination of first-principles calculations and multimodal spectroscopy analysis. Our calculations show that nonsolvated [Mg(TFSI)]+ is the strongest adsorbing species on the MgV2O4 surface compared with all other ions while partially solvated [Mg(TFSI):G2]+ is the most reactive species. The cleavage of C-S bonds in TFSI- to form CF3- is predicted to be the 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 with 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 a MgV2O4 thin film to form a well-defined electrolyte-MgV2O4 interface. Analysis of the soft-landed interface 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) and the higher amount of MgFx with [Mg(TFSI):G2]+ formed in the interfacial region, which corroborates the theoretical observation. Overall, these results indicate that Mg2+ desolvation results in electrolyte decomposition facilitated by surface adsorption, charge transfer, and the formation of passivating fluorides on the MgV2O4 cathode surface. This work provides the first evidence of the primary mechanisms leading to electrolyte decomposition at high-voltage oxide surfaces in multivalent batteries and suggests that the design of new, anodically stable electrolytes must target systems that facilitate cation desolvation.

KW - Cathode-electrolyte interphase formation

KW - Density functional theory

KW - MgVO cathode

KW - ion soft landing

KW - surface reactivity

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U2 - 10.1021/acsami.3c07875

DO - 10.1021/acsami.3c07875

M3 - Article

C2 - 37805993

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SN - 1944-8244

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EP - 48084

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

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