Electrolyte Reactivity on the MgV2O4 Cathode Surface

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

doi:10.1021/acsami.3c07875

Title: Electrolyte Reactivity on the MgV₂O₄ Cathode Surface

Journal Article · Sun Oct 08 00:00:00 EDT 2023 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.3c07875· OSTI ID:2328492

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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)

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.

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Research Organization:: 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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: AC05-76RL01830; AC02-06CH11357; AC02-05CH11231; DMR-2308691; ECCS-1542205; ECCS-2025633; DMR-1720139; DMR-0959470; DMR-1626065

OSTI ID:: 2328492

Report Number(s):: PNNL-SA-185103

Journal Information:: ACS Applied Materials and Interfaces, Vol. 15, Issue 41; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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25 ENERGY STORAGE
surface reactivity
ion soft landing
MgV2O4 cathode
Density functional theory
Cathode-electrolyte interphase formation

Title: Electrolyte Reactivity on the MgV2O4 Cathode Surface

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Title: Electrolyte Reactivity on the MgV₂O₄ Cathode Surface