DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Investigating the Effects of Lithium Phosphorous Oxynitride Coating on Blended Solid Polymer Electrolytes

Abstract

Solid-state electrolytes are very promising to enhance the safety of lithium ion batteries. Two classes of solid electrolytes, polymer and ceramic, can be combined to yield a hybrid electrolyte that can synergistically combine the properties of both materials. Chemical stability, thermal stability, and high mechanical modulus of ceramic electrolytes against dendrite penetration can be combined with the flexibility and ease of processing of polymer electrolytes. By laminating a polymer electrolyte with a ceramic electrolyte, the stability of the solid electrolyte is expected to improve against lithium metal, and the ionic conductivity could remain close to the value of the original polymer electrolyte as long as an appropriate thickness of the ceramic electrolyte is applied. In this paper we report a bilayered lithium-ion conducting hybrid solid electrolyte consisting of a blended polymer electrolyte (BPE) laminated with a thin layer of the inorganic solid electrolyte lithium phosphorous oxynitride (LiPON). The hybrid system was thoroughly studied. First, we investigated the influence of polymer chain length and lithium salt ratio on the ionic conductivity of the BPE based on poly(ethylene oxide) (PEO) and poly(propylene carbonate) (PPC) with the salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The optimized BPE consisted of 100k molecular weight PEO, 50k molecular weightmore » PPC, and 25(w/w)% LiTFSI, (denoted as PEO100PPC50LiTFSI25) which exhibited an ionic conductivity of 2.11×10-5 S/cm, and the ionic conductivity showed no thermal memory effects as the PEO crystallites were well disrupted by PPC and LiTFSI. Secondly, the effects of LiPON coating on the BPE were evaluated as a function of thickness down to 20 nm. The resulting bilayer structure showed an increase in the voltage window from 5.2 to 5.5 V (vs Li/Li+) and thermal activation energies that approached the activation energy of the BPE when thinner LiPON layers were used, resulting in similar ionic conductivities for 30 nm LiPON coatings on PEO100PPC50LiTFSI25. Coating BPEs with a thin layer of LiPON is shown to be an effective strategy to improve the long-term stability against lithium.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [3];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. National Renewable Energy Laboratory, Materials Science Center, Golden, Colorado 80401, United States, Department of Chemical Engineering, Institute for Materials Research and Innovation, University of Louisiana Lafayette, Lafayette, Louisiana 70504, United States
  2. National Renewable Energy Laboratory, Materials Science Center, Golden, Colorado 80401, United States
  3. Department of Chemical Engineering, Institute for Materials Research and Innovation, University of Louisiana Lafayette, Lafayette, Louisiana 70504, United States
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF); Chevron Corporation; USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
2316079
Alternate Identifier(s):
OSTI ID: 1660221
Report Number(s):
NREL/JA-5K00-76378
Journal ID: ISSN 1944-8244
Grant/Contract Number:  
AC36-08GO28308; 1832963
Resource Type:
Published Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Name: ACS Applied Materials and Interfaces Journal Volume: 12 Journal Issue: 36; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; ceramic; lithium ion batteries; polymer; solid state electrolytes

Citation Formats

LaCoste, Jed, Li, Zhifei, Xu, Yun, He, Zizhou, Matherne, Drew, Zakutayev, Andriy, and Fei, Ling. Investigating the Effects of Lithium Phosphorous Oxynitride Coating on Blended Solid Polymer Electrolytes. United States: N. p., 2020. Web. doi:10.1021/acsami.0c09113.
LaCoste, Jed, Li, Zhifei, Xu, Yun, He, Zizhou, Matherne, Drew, Zakutayev, Andriy, & Fei, Ling. Investigating the Effects of Lithium Phosphorous Oxynitride Coating on Blended Solid Polymer Electrolytes. United States. https://doi.org/10.1021/acsami.0c09113
LaCoste, Jed, Li, Zhifei, Xu, Yun, He, Zizhou, Matherne, Drew, Zakutayev, Andriy, and Fei, Ling. Thu . "Investigating the Effects of Lithium Phosphorous Oxynitride Coating on Blended Solid Polymer Electrolytes". United States. https://doi.org/10.1021/acsami.0c09113.
@article{osti_2316079,
title = {Investigating the Effects of Lithium Phosphorous Oxynitride Coating on Blended Solid Polymer Electrolytes},
author = {LaCoste, Jed and Li, Zhifei and Xu, Yun and He, Zizhou and Matherne, Drew and Zakutayev, Andriy and Fei, Ling},
abstractNote = {Solid-state electrolytes are very promising to enhance the safety of lithium ion batteries. Two classes of solid electrolytes, polymer and ceramic, can be combined to yield a hybrid electrolyte that can synergistically combine the properties of both materials. Chemical stability, thermal stability, and high mechanical modulus of ceramic electrolytes against dendrite penetration can be combined with the flexibility and ease of processing of polymer electrolytes. By laminating a polymer electrolyte with a ceramic electrolyte, the stability of the solid electrolyte is expected to improve against lithium metal, and the ionic conductivity could remain close to the value of the original polymer electrolyte as long as an appropriate thickness of the ceramic electrolyte is applied. In this paper we report a bilayered lithium-ion conducting hybrid solid electrolyte consisting of a blended polymer electrolyte (BPE) laminated with a thin layer of the inorganic solid electrolyte lithium phosphorous oxynitride (LiPON). The hybrid system was thoroughly studied. First, we investigated the influence of polymer chain length and lithium salt ratio on the ionic conductivity of the BPE based on poly(ethylene oxide) (PEO) and poly(propylene carbonate) (PPC) with the salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The optimized BPE consisted of 100k molecular weight PEO, 50k molecular weight PPC, and 25(w/w)% LiTFSI, (denoted as PEO100PPC50LiTFSI25) which exhibited an ionic conductivity of 2.11×10-5 S/cm, and the ionic conductivity showed no thermal memory effects as the PEO crystallites were well disrupted by PPC and LiTFSI. Secondly, the effects of LiPON coating on the BPE were evaluated as a function of thickness down to 20 nm. The resulting bilayer structure showed an increase in the voltage window from 5.2 to 5.5 V (vs Li/Li+) and thermal activation energies that approached the activation energy of the BPE when thinner LiPON layers were used, resulting in similar ionic conductivities for 30 nm LiPON coatings on PEO100PPC50LiTFSI25. Coating BPEs with a thin layer of LiPON is shown to be an effective strategy to improve the long-term stability against lithium.},
doi = {10.1021/acsami.0c09113},
journal = {ACS Applied Materials and Interfaces},
number = 36,
volume = 12,
place = {United States},
year = {Thu Aug 13 00:00:00 EDT 2020},
month = {Thu Aug 13 00:00:00 EDT 2020}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsami.0c09113

Save / Share:

Works referenced in this record:

Investigation of the local structure of LiPON thin films to better understand the role of nitrogen on their performance
journal, March 2011


High‐performance solid PEO/PPC/LLTO‐nanowires polymer composite electrolyte for solid‐state lithium battery
journal, May 2019

  • Zhu, Lin; Zhu, Penghui; Yao, Shanshan
  • International Journal of Energy Research, Vol. 43, Issue 9
  • DOI: 10.1002/er.4638

Ionic conductivities and structure of lithium phosphorus oxynitride glasses
journal, April 1995


Lithium ion conductivity in lithium nitride
journal, September 1976


Chemical and microstructural modifications in LiPON thin films exposed to atmospheric humidity
journal, March 2011


Structural and ionic conductivity of PEO blend PEG solid polymer electrolyte
journal, January 2006


A review of lithium and non-lithium based solid state batteries
journal, May 2015


Sandwich-Like Poly(propylene carbonate)-Based Electrolyte for Ambient-Temperature Solid-State Lithium Ion Batteries
journal, November 2017


Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries
journal, January 2016

  • Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep19892

Bi-layer lithium phosphorous oxynitride/aluminium substituted lithium lanthanum titanate as a promising solid electrolyte for long-life rechargeable lithium–oxygen batteries
journal, January 2015

  • Le, Hang T. T.; Kalubarme, Ramchandra S.; Ngo, Duc Tung
  • Journal of Materials Chemistry A, Vol. 3, Issue 44
  • DOI: 10.1039/C5TA06374D

The pursuit of solid-state electrolytes for lithium batteries: from comprehensive insight to emerging horizons
journal, January 2016

  • Chen, Renjie; Qu, Wenjie; Guo, Xing
  • Materials Horizons, Vol. 3, Issue 6
  • DOI: 10.1039/C6MH00218H

Enhancement of Li Ion Conductivity by Electrospun Polymer Fibers and Direct Fabrication of Solvent-Free Separator Membranes for Li Ion Batteries
journal, February 2017


In Situ Generation of Poly (Vinylene Carbonate) Based Solid Electrolyte with Interfacial Stability for LiCoO 2 Lithium Batteries
journal, November 2016


Assessing structure and stability of polymer/lithium-metal interfaces from first-principles calculations
journal, January 2019

  • Ebadi, Mahsa; Marchiori, Cleber; Mindemark, Jonas
  • Journal of Materials Chemistry A, Vol. 7, Issue 14
  • DOI: 10.1039/C8TA12147H

Fabrication and characterization of PEO/PPC polymer electrolyte for lithium-ion battery
journal, March 2010

  • Yu, Xiao-Yuan; Xiao, Min; Wang, Shuang-Jin
  • Journal of Applied Polymer Science, Vol. 115, Issue 5
  • DOI: 10.1002/app.29915

Solid Electrolyte Lithium Phosphous Oxynitride as a Protective Nanocladding Layer for 3D High-Capacity Conversion Electrodes
journal, January 2016


Lithium bis(fluorosulfonyl)imide/poly(ethylene oxide) polymer electrolyte
journal, July 2014


Solid electrolyte coated high voltage layered–layered lithium-rich composite cathode: Li1.2Mn0.525Ni0.175Co0.1O2
journal, January 2013

  • Martha, Surendra K.; Nanda, Jagjit; Kim, Yoongu
  • Journal of Materials Chemistry A, Vol. 1, Issue 18
  • DOI: 10.1039/c3ta10586e

Characteristics of lithium phosphorous oxynitride thin films deposited by metal-organic chemical vapor deposition technique
journal, December 2013


Preparation, structure and ionic conductivity of lithium phosphide
journal, April 1989


Transport Properties of the Solid Polymer Electrolyte System P(EO) n LiTFSI
journal, April 2000

  • Edman, Ludvig; Doeff, Marca M.; Ferry, Anders
  • The Journal of Physical Chemistry B, Vol. 104, Issue 15
  • DOI: 10.1021/jp993897z

Mechanical characterization of LiPON films using nanoindentation
journal, October 2011


Interface reactions between LiPON and lithium studied by in-situ X-ray photoemission
journal, May 2015


Physical properties of solid polymer electrolyte PEO(LiTFSI) complexes
journal, August 1995


Ionic conductivity studies of 49% poly(methyl methacrylate)-grafted natural rubber-based solid polymer electrolytes
journal, October 2008


Structural and Compositional Factors That Control the Li-Ion Conductivity in LiPON Electrolytes
journal, September 2018


Radio-Frequency Magnetron Sputtering Power Effect on the Ionic Conductivities of Lipon Films
journal, January 2002

  • Choi, C. H.; Cho, W. I.; Cho, B. W.
  • Electrochemical and Solid-State Letters, Vol. 5, Issue 1
  • DOI: 10.1149/1.1420926

Study on ionic conductivity and dielectric properties of PEO-based solid nanocomposite polymer electrolytes
journal, March 2017


Ionic Transport Across Interfaces of Solid Glass and Polymer Electrolytes for Lithium Ion Batteries
journal, January 2011

  • Tenhaeff, W. E.; Yu, X.; Hong, K.
  • Journal of The Electrochemical Society, Vol. 158, Issue 10
  • DOI: 10.1149/1.3625281

Effect of molecular weight on conductivity of polymer electrolytes
journal, November 2011

  • Teran, Alexander A.; Tang, Maureen H.; Mullin, Scott A.
  • Solid State Ionics, Vol. 203, Issue 1
  • DOI: 10.1016/j.ssi.2011.09.021

Preparation of new composite polymer electrolyte for long cycling all-solid-state lithium battery
journal, January 2019