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Title: Revealing Nanoscale Solid–Solid Interfacial Phenomena for Long-Life and High-Energy All-Solid-State Batteries

Abstract

Enabling long cyclability of high-voltage oxide cathodes is a persistent challenge for all-solid-state batteries, largely because of their poor interfacial stabilities against sulfide solid electrolytes. While protective oxide coating layers such as LiNbO3 (LNO) have been proposed, its precise working mechanisms are still not fully understood. Existing literature attributes reductions in interfacial impedance growth to the coating's ability to prevent interfacial reactions. However, its true nature is more complex, with cathode interfacial reactions and electrolyte electrochemical decomposition occurring simultaneously, making it difficult to decouple each effect. Herein, we utilized various advanced characterization tools and first-principles calculations to probe the interfacial phenomenon between solid electrolyte Li6PS5Cl (LPSCl) and high-voltage cathode LiNi0.85Co0.1Al0.05O2 (NCA). We segregated the effects of spontaneous reaction between LPSCl and NCA at the interface and quantified the intrinsic electrochemical decomposition of LPSCl during cell cycling. Both experimental and computational results demonstrated improved thermodynamic stability between NCA and LPSCl after incorporation of the LNO coating. Additionally, we revealed the in situ passivation effect of LPSCl electrochemical decomposition. When combined, both these phenomena occurring at the first charge cycle result in a stabilized interface, enabling long cyclability of all-solid-state batteries.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [2];  [2];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, San Diego, La Jolla, CA (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
LG Chem; Shell E&P Co; Sustainable Power and Energy Center (SPEC); National Science Foundation (NSF); USDOE Office of Science (SC)
OSTI Identifier:
1606549
Alternate Identifier(s):
OSTI ID: 1737586
Grant/Contract Number:  
AC02-06CH11357; PT78832; CHE-1338173; ECCS-1542148; AC02-05CH11231; ACI-1548562
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 11; Journal Issue: 46; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Li6PS5Cl (LPSCl); LiNbO3 coating; LiNi0.85Co0.1Al0.05O2 (NCA); ab initio molecular dynamics (AIMD); interface; interfacial engineering; solid electrolyte; solid-state battery; density functional theory (DFT) calculations

Citation Formats

Banerjee, Abhik, Tang, Hanmei, Wang, Xuefeng, Cheng, Ju-Hsiang, Nguyen, Han, Zhang, Minghao, Tan, Darren H. S., Wynn, Thomas A., Wu, Erik A., Doux, Jean-Marie, Wu, Tianpin, Ma, Lu, Sterbinsky, George E., D’Souza, Macwin Savio, Ong, Shyue Ping, and Meng, Ying Shirley. Revealing Nanoscale Solid–Solid Interfacial Phenomena for Long-Life and High-Energy All-Solid-State Batteries. United States: N. p., 2019. Web. doi:10.1021/acsami.9b13955.
Banerjee, Abhik, Tang, Hanmei, Wang, Xuefeng, Cheng, Ju-Hsiang, Nguyen, Han, Zhang, Minghao, Tan, Darren H. S., Wynn, Thomas A., Wu, Erik A., Doux, Jean-Marie, Wu, Tianpin, Ma, Lu, Sterbinsky, George E., D’Souza, Macwin Savio, Ong, Shyue Ping, & Meng, Ying Shirley. Revealing Nanoscale Solid–Solid Interfacial Phenomena for Long-Life and High-Energy All-Solid-State Batteries. United States. https://doi.org/10.1021/acsami.9b13955
Banerjee, Abhik, Tang, Hanmei, Wang, Xuefeng, Cheng, Ju-Hsiang, Nguyen, Han, Zhang, Minghao, Tan, Darren H. S., Wynn, Thomas A., Wu, Erik A., Doux, Jean-Marie, Wu, Tianpin, Ma, Lu, Sterbinsky, George E., D’Souza, Macwin Savio, Ong, Shyue Ping, and Meng, Ying Shirley. Wed . "Revealing Nanoscale Solid–Solid Interfacial Phenomena for Long-Life and High-Energy All-Solid-State Batteries". United States. https://doi.org/10.1021/acsami.9b13955. https://www.osti.gov/servlets/purl/1606549.
@article{osti_1606549,
title = {Revealing Nanoscale Solid–Solid Interfacial Phenomena for Long-Life and High-Energy All-Solid-State Batteries},
author = {Banerjee, Abhik and Tang, Hanmei and Wang, Xuefeng and Cheng, Ju-Hsiang and Nguyen, Han and Zhang, Minghao and Tan, Darren H. S. and Wynn, Thomas A. and Wu, Erik A. and Doux, Jean-Marie and Wu, Tianpin and Ma, Lu and Sterbinsky, George E. and D’Souza, Macwin Savio and Ong, Shyue Ping and Meng, Ying Shirley},
abstractNote = {Enabling long cyclability of high-voltage oxide cathodes is a persistent challenge for all-solid-state batteries, largely because of their poor interfacial stabilities against sulfide solid electrolytes. While protective oxide coating layers such as LiNbO3 (LNO) have been proposed, its precise working mechanisms are still not fully understood. Existing literature attributes reductions in interfacial impedance growth to the coating's ability to prevent interfacial reactions. However, its true nature is more complex, with cathode interfacial reactions and electrolyte electrochemical decomposition occurring simultaneously, making it difficult to decouple each effect. Herein, we utilized various advanced characterization tools and first-principles calculations to probe the interfacial phenomenon between solid electrolyte Li6PS5Cl (LPSCl) and high-voltage cathode LiNi0.85Co0.1Al0.05O2 (NCA). We segregated the effects of spontaneous reaction between LPSCl and NCA at the interface and quantified the intrinsic electrochemical decomposition of LPSCl during cell cycling. Both experimental and computational results demonstrated improved thermodynamic stability between NCA and LPSCl after incorporation of the LNO coating. Additionally, we revealed the in situ passivation effect of LPSCl electrochemical decomposition. When combined, both these phenomena occurring at the first charge cycle result in a stabilized interface, enabling long cyclability of all-solid-state batteries.},
doi = {10.1021/acsami.9b13955},
journal = {ACS Applied Materials and Interfaces},
number = 46,
volume = 11,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: Schematic of interfacial study in this work. The chemical reactions at LiNi0.85Co0.1Al0.05O2 (NCA) | Li6PS5Cl (LPSCl) interface, and electrochemical decomposition of LPSCl were segregated and their reaction products explored with both experimental tools and computation. The oLPSCl is referred to the oxidized LPSCl.

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