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Title: Kinetics-Controlled Degradation Reactions at Crystalline LiPON/Li xCoO 2 and Crystalline LiPON/Li-Metal Interfaces

Detailed understanding of solid–solid interface structure–function relationships is critical for the improvement and wide deployment of all-solid-state batteries. The interfaces between lithium phosphorous oxynitride (LiPON) solid electrolyte material and lithium metal anode, and between LiPON and Li xCoO 2 cathode, have been reported to generate solid–electrolyte interphase (SEI)-like products and/or disordered regions. In this paper, using electronic structure calculations and crystalline LiPON models, we predict that LiPON models with purely P-N-P backbones are kinetically inert towards lithium at room temperature. In contrast, transfer of oxygen atoms from low-energy Li xCoO 2(104) surfaces to LiPON is much faster under ambient conditions. The mechanisms of the primary reaction steps, LiPON structural motifs that readily reacts with lithium metal, experimental results on amorphous LiPON to partially corroborate these predictions, and possible mitigation strategies to reduce degradations are discussed. Finally, LiPON interfaces are found to be useful case studies for highlighting the importance of kinetics-controlled processes during battery assembly at moderate processing temperatures.
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [3] ;  [2] ;  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Univ. of Maryland, College Park, MD (United States). Dept. of Materials Science and Engineering
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Publication Date:
Report Number(s):
SAND2018-9824J
Journal ID: ISSN 1864-5631; 667679
Grant/Contract Number:
NA0003525; SC0001160
Type:
Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 11; Journal Issue: 12; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Univ. of Maryland, College Park, MD (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; ab initio calculations; batteries; interfaces; LiPON; solid-solid reactions
OSTI Identifier:
1473925
Alternate Identifier(s):
OSTI ID: 1433554

Leung, Kevin, Pearse, Alexander J., Talin, A. Alec, Fuller, Elliot J., Rubloff, Gary W., and Modine, Normand A.. Kinetics-Controlled Degradation Reactions at Crystalline LiPON/LixCoO2 and Crystalline LiPON/Li-Metal Interfaces. United States: N. p., Web. doi:10.1002/cssc.201800027.
Leung, Kevin, Pearse, Alexander J., Talin, A. Alec, Fuller, Elliot J., Rubloff, Gary W., & Modine, Normand A.. Kinetics-Controlled Degradation Reactions at Crystalline LiPON/LixCoO2 and Crystalline LiPON/Li-Metal Interfaces. United States. doi:10.1002/cssc.201800027.
Leung, Kevin, Pearse, Alexander J., Talin, A. Alec, Fuller, Elliot J., Rubloff, Gary W., and Modine, Normand A.. 2018. "Kinetics-Controlled Degradation Reactions at Crystalline LiPON/LixCoO2 and Crystalline LiPON/Li-Metal Interfaces". United States. doi:10.1002/cssc.201800027.
@article{osti_1473925,
title = {Kinetics-Controlled Degradation Reactions at Crystalline LiPON/LixCoO2 and Crystalline LiPON/Li-Metal Interfaces},
author = {Leung, Kevin and Pearse, Alexander J. and Talin, A. Alec and Fuller, Elliot J. and Rubloff, Gary W. and Modine, Normand A.},
abstractNote = {Detailed understanding of solid–solid interface structure–function relationships is critical for the improvement and wide deployment of all-solid-state batteries. The interfaces between lithium phosphorous oxynitride (LiPON) solid electrolyte material and lithium metal anode, and between LiPON and LixCoO2 cathode, have been reported to generate solid–electrolyte interphase (SEI)-like products and/or disordered regions. In this paper, using electronic structure calculations and crystalline LiPON models, we predict that LiPON models with purely P-N-P backbones are kinetically inert towards lithium at room temperature. In contrast, transfer of oxygen atoms from low-energy LixCoO2(104) surfaces to LiPON is much faster under ambient conditions. The mechanisms of the primary reaction steps, LiPON structural motifs that readily reacts with lithium metal, experimental results on amorphous LiPON to partially corroborate these predictions, and possible mitigation strategies to reduce degradations are discussed. Finally, LiPON interfaces are found to be useful case studies for highlighting the importance of kinetics-controlled processes during battery assembly at moderate processing temperatures.},
doi = {10.1002/cssc.201800027},
journal = {ChemSusChem},
number = 12,
volume = 11,
place = {United States},
year = {2018},
month = {3}
}

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