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Voltage-Dependent First-Principles Barriers to Li Transport within Li-Ion Battery Solid Electrolyte Interphases

Journal Article · · Journal of Physical Chemistry. C
 [1]
  1. Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Charging a Li-ion battery requires Li-ion transport between the cathode and the anode. This Li-ion transport is dependent on (among other factors) the electrostatic environment that the ion encounters within the solid electrolyte interphase (SEI), which separates the anode from the surrounding electrolyte. A previous first-principles work has illuminated the reaction barriers through likely atomistic SEI environments but has had difficulty accurately reflecting the larger electrostatic potential landscape that an ion encounters moving through the SEI. In this work, we apply the recently developed quantum continuum approximation (QCA) technique to provide an equilibrium electronic potentiostat for first-principles interface calculations. Using QCA, we calculate the potential barrier for Li-ion transport through LiF, Li2O, and Li2CO3 SEIs along with LiF–LiF and LiF–Li2O grain boundaries, all paired with Li metal anodes. Here, we demonstrate that the SEI potential barrier is dependent on the electrochemical potentials of the anode in each system. Finally, we use these techniques to estimate the change in the diffusion barrier for a Li ion moving in a LiF SEI as a function of the anode potential. We find that properly accounting for interface and electronic voltage effects significantly lowers reaction barriers compared with previous literature results.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
NA0003525
OSTI ID:
2394699
Report Number(s):
SAND--2024-08352J
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 25 Vol. 128; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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