Uncorrelated Lithium-Ion Hopping in a Dynamic Solvent-Anion Network

Lithium batteries rely crucially on fast charge and mass transport of Li+ in the electrolyte. For liquid and polymer electrolytes with added lithium salts, Li+ couples to the counter-anion to form ionic clusters that produce inefficient Li+ transport and lead to Li dendrite formation. Quantification of Li+ transport in glycerol-salt electrolytes via NMR experiments and MD simulations reveals a surprising Li+-hopping mechanism. The Li+ transference number, measured by ion-specific electrophoretic NMR, can reach 0.7, and Li+ diffusion does not correlate with nearby ion motions, even at high salt concentration. Glycerol’s high density of hydroxyl groups increases ion dissociation and slows anion diffusion, while the close proximity of hydroxyls and anions lowers local energy barriers, facilitating Li+ hopping. This system represents a bridge between liquid and inorganic solid electrolytes, thus motivating new molecular designs for liquid and polymer electrolytes to enable the uncorrelated Li+-hopping transport needed for fast-charging and all-solid-state batteries.

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Work Title Uncorrelated Lithium-Ion Hopping in a Dynamic Solvent-Anion Network
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Open Access
Creators
  1. Deyang Yu
  2. Diego Troya
  3. Andrew G. Korovich
  4. Joshua E. Bostwick
  5. Ralph H. Colby
  6. Louis A. Madsen
Keyword
  1. Anion
  2. Ions
  3. Electrolytes
  4. Ion
  5. Lithium
  6. Negative Ions
  7. Glycerol
  8. Diffusion
  9. Salts
  10. Liquids
  11. Mass Transfer
  12. Charge Transfer
  13. Dissociation
  14. Energy Barrier
  15. Liquid
  16. Hydroxyl
  17. Molecular Cluster
  18. Transference Number
  19. Simulation
  20. Polymers
  21. Nuclear Magnetic Resonance
  22. Lithium Salt
  23. Solid Electrolyte
  24. Experiments
  25. Solid State Batteries
  26. Energy Barriers
  27. Solid Electrolytes
  28. Lithium Batteries
  29. Dendrites (Metallography)
License CC BY 4.0 (Attribution)
Work Type Article
Publisher
  1. ACS Energy Letters
Publication Date March 28, 2023
Publisher Identifier (DOI)
  1. 10.1021/acsenergylett.3c00454
Related URLs
Deposited October 22, 2024

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Version 1
published

  • Created
  • Updated
  • Added Creator Deyang Yu
  • Added Creator Diego Troya
  • Added Creator Andrew G. Korovich
  • Added Creator Joshua E. Bostwick
  • Added Creator Ralph H. Colby
  • Added Creator Louis A. Madsen
  • Updated Work Title, Keyword, Publisher, and 4 more Show Changes
    Work Title
    • Uncorrelated lithium-ion hopping in a dynamic solvent-anion network
    • Uncorrelated Lithium-Ion Hopping in a Dynamic Solvent-Anion Network
    Keyword
    • Anion, Ions, Electrolytes, Ion, Lithium, Negative Ions, Glycerol, Diffusion, Salts, Liquids, Mass Transfer, Charge Transfer, Dissociation, Energy Barrier, Liquid, Hydroxyl, Molecular Cluster, Transference Number, Simulation, Polymers, Nuclear Magnetic Resonance, Lithium Salt, Solid Electrolyte, Experiments, Solid State Batteries, Energy Barriers, Solid Electrolytes, Lithium Batteries, Dendrites (Metallography)
    Publisher
    • ACS Energy Letters
    Publisher Identifier (DOI)
    • 10.1021/acsenergylett.3c00454
    Related URLs
    • https://doi.org/10.1021/acsenergylett.3c00454
    Description
    • <p>Lithium batteries rely crucially on fast charge and mass transport of Li<sup>+</sup> in the electrolyte. For liquid and polymer electrolytes with added lithium salts, Li<sup>+</sup> couples to the counter-anion to form ionic clusters that produce inefficient Li<sup>+</sup> transport and lead to Li dendrite formation. Quantification of Li<sup>+</sup> transport in glycerol-salt electrolytes via NMR experiments and MD simulations reveals a surprising Li<sup>+</sup>-hopping mechanism. The Li<sup>+</sup> transference number, measured by ion-specific electrophoretic NMR, can reach 0.7, and Li<sup>+</sup> diffusion does not correlate with nearby ion motions, even at high salt concentration. Glycerol’s high density of hydroxyl groups increases ion dissociation and slows anion diffusion, while the close proximity of hydroxyls and anions lowers local energy barriers, facilitating Li<sup>+</sup> hopping. This system represents a bridge between liquid and inorganic solid electrolytes, thus motivating new molecular designs for liquid and polymer electrolytes to enable the uncorrelated Li<sup>+</sup>-hopping transport needed for fast-charging and all-solid-state batteries.</p>
    Publication Date
    • 2023-04-14
  • Updated
  • Updated
  • Updated Creator Deyang Yu
  • Updated Creator Diego Troya
  • Updated Creator Andrew G. Korovich
  • Updated Creator Joshua E. Bostwick
  • Updated Creator Ralph H. Colby
  • Updated Creator Louis A. Madsen
  • Added Madsen_LithiumIonHopping_Manuscript_Accepted2023EnergyLetters.pdf
  • Updated License Show Changes
    License
    • https://creativecommons.org/licenses/by/4.0/
  • Published
  • Updated
  • Updated Publication Date Show Changes
    Publication Date
    • 2023-04-14
    • 2023-03-28