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Title: Stability and conductivity of cation- and anion-substituted LiBH 4 -based solid-state electrolytes

Abstract

The high-temperature phase of LiBH4 (HT-LiBH4) exhibits a promisingly high lithium ion conductivity but is unstable at room temperature. We use density functional theory (DFT) calculations to investigate the stabilization effect of halogen and alkali cation/anion substitutions on HT-LiBH4 as well the underlying mechanism for the high lithium ion conductivity. We find that increasing the substituent concentration enhances the stabilization of HT-LiBH4 (i.e., the DFT energy difference between the low- and high-temperature forms of substituted LiBH4 is reduced). Cation/anion substitution also leads to a higher Li defect (vacancy, interstitial, and Frenkel) formation energy, thereby reducing the Li defect (vacancy, interstitial, and Frenkel) concentrations. Using DFT migration barriers input into kinetic Monte Carlo simulations and the Materials INTerface (MINT) framework, here we calculate the room-temperature lithium ion conductivities for Li(BH4)1-xIx (x = 0.25 and 0.5) and Li1-yKyBH4 (y = 0.25). Our calculations suggest that the lower I concentration leads to a higher lithium ion conductivity of 5.7 x10-3 S/cm compared with that of Li(BH4)0.5I0.5 (4.2 ×10-5 S/cm) because of the formation of more Li-related defects. Based on our findings, we suggest that the stabilization of HT-LiBH4-based lithium ion conductors can be controlled by carefully tuning the cation/anion substituent concentrations to maximizemore » the lithium ionic conductivities of the specific system.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
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  1. Northwestern University, Evanston, IL (United States)
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institute of Standards and Technology (NIST); Dow Chemical Company
OSTI Identifier:
1541391
Alternate Identifier(s):
OSTI ID: 1454898
Grant/Contract Number:  
FG02-07ER46433; AC02-05CH11231; AC02-06CH11357; 70NANB14H012; DEAC02-06CH11357; DEFG02-07ER46433
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 6; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ionic transport; density functional theory

Citation Formats

Yao, Zhenpeng, Kim, Soo, Michel, Kyle, Zhang, Yongsheng, Aykol, Muratahan, and Wolverton, Chris. Stability and conductivity of cation- and anion-substituted LiBH4 -based solid-state electrolytes. United States: N. p., 2018. Web. doi:10.1103/physrevmaterials.2.065402.
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Yao, Zhenpeng, Kim, Soo, Michel, Kyle, Zhang, Yongsheng, Aykol, Muratahan, & Wolverton, Chris. Stability and conductivity of cation- and anion-substituted LiBH4 -based solid-state electrolytes. United States. https://doi.org/10.1103/physrevmaterials.2.065402
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Yao, Zhenpeng, Kim, Soo, Michel, Kyle, Zhang, Yongsheng, Aykol, Muratahan, and Wolverton, Chris. Tue . "Stability and conductivity of cation- and anion-substituted LiBH4 -based solid-state electrolytes". United States. https://doi.org/10.1103/physrevmaterials.2.065402. https://www.osti.gov/servlets/purl/1541391.
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@article{osti_1541391,
title = {Stability and conductivity of cation- and anion-substituted LiBH4 -based solid-state electrolytes},
author = {Yao, Zhenpeng and Kim, Soo and Michel, Kyle and Zhang, Yongsheng and Aykol, Muratahan and Wolverton, Chris},
abstractNote = {The high-temperature phase of LiBH4 (HT-LiBH4) exhibits a promisingly high lithium ion conductivity but is unstable at room temperature. We use density functional theory (DFT) calculations to investigate the stabilization effect of halogen and alkali cation/anion substitutions on HT-LiBH4 as well the underlying mechanism for the high lithium ion conductivity. We find that increasing the substituent concentration enhances the stabilization of HT-LiBH4 (i.e., the DFT energy difference between the low- and high-temperature forms of substituted LiBH4 is reduced). Cation/anion substitution also leads to a higher Li defect (vacancy, interstitial, and Frenkel) formation energy, thereby reducing the Li defect (vacancy, interstitial, and Frenkel) concentrations. Using DFT migration barriers input into kinetic Monte Carlo simulations and the Materials INTerface (MINT) framework, here we calculate the room-temperature lithium ion conductivities for Li(BH4)1-xIx (x = 0.25 and 0.5) and Li1-yKyBH4 (y = 0.25). Our calculations suggest that the lower I concentration leads to a higher lithium ion conductivity of 5.7 x10-3 S/cm compared with that of Li(BH4)0.5I0.5 (4.2 ×10-5 S/cm) because of the formation of more Li-related defects. Based on our findings, we suggest that the stabilization of HT-LiBH4-based lithium ion conductors can be controlled by carefully tuning the cation/anion substituent concentrations to maximize the lithium ionic conductivities of the specific system.},
doi = {10.1103/physrevmaterials.2.065402},
journal = {Physical Review Materials},
number = 6,
volume = 2,
place = {United States},
year = {Tue Jun 19 00:00:00 EDT 2018},
month = {Tue Jun 19 00:00:00 EDT 2018}
}
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