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Title: From Bulk to Interface: Solvent Exchange Dynamics and Their Role in Ion Transport and the Interfacial Model of Rechargeable Magnesium Batteries

Journal Article · · Journal of the American Chemical Society
ORCiD logo [1];  [2];  [1]; ORCiD logo [1]; ORCiD logo [3];  [4];  [5]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [6]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Joint Center for Energy Storage Research (JCESR)
  2. Stony Brook Univ., NY (United States)
  3. Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research (JCESR)
  4. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Joint Center for Energy Storage Research (JCESR); Sogang Univ. Seoul (Korea, Republic of)
  5. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  6. Sogang Univ. Seoul (Korea, Republic of)
+ Show Author Affiliations

Multivalent battery chemistries have been explored in response to the increasing demand for high-energy rechargeable batteries utilizing sustainable resources. Solvation structures of working cations have been recognized as a key component in the design of electrolytes; however, most structure–property correlations of metal ions in organic electrolytes usually build upon favorable static solvation structures, often overlooking solvent exchange dynamics. We here report the ion solvation structures and solvent exchange rates of magnesium electrolytes in various solvents by using multimodal nuclear magnetic resonance (NMR) analysis and molecular dynamics/density functional theory (MD/DFT) calculations. These magnesium solvation structures and solvent exchange dynamics are correlated to the combined effects of several physicochemical properties of the solvents. Moreover, Mg2+ transport and interfacial charge transfer efficiency are found to be closely correlated to the solvent exchange rate in the binary electrolytes where the solvent exchange is tunable by the fraction of diluent solvents. Our primary findings are (1) most battery-related solvents undergo ultraslow solvent exchange coordinating to Mg2+ (with time scales ranging from 0.5 μs to 5 ms), (2) the cation transport mechanism is a mixture of vehicular and structural diffusion even at the ultraslow exchange limit (with faster solvent exchange leading to faster cation transport), and (3) an interfacial model wherein organic-rich regions facilitate desolvation and inorganic regions promote Mg2+ transport is consistent with our NMR, electrochemistry, and cryogenic X-ray photoelectron spectroscopy (cryo-XPS) results. In conclusion, this observed ultraslow solvent exchange and its importance for ion transport and interfacial properties necessitate the judicious selection of solvents and informed design of electrolyte blends for multivalent electrolytes.

Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
NA0003525; AC05-76RL01830
OSTI ID:
2472751
Report Number(s):
SAND--2024-13782J
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 19 Vol. 146; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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