skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Garnet-rich composite solid electrolytes for dendrite-free, high-rate, solid-state lithium-metal batteries

Journal Article · · Energy Storage Materials

Composite solid electrolytes (CSEs), which are composed of inorganic fillers and organic polymers, show improved safety and suppressed lithium dendrite growth in Li-metal batteries, as compared to flammable liquid electrolytes. However, the performance of current CSEs is limited by the agglomeration effect, with low content of inorganic Li+-conducting fillers and ineffective Li+ transport between the inorganic fillers and the polymer matrix. To address these challenges, a new type of CSE composed of silane-modified Li6.28La3Al0.24Zr2O12 (s@LLAZO) nanofibers and poly(ethylene glycol) diacrylate (PEGDA) is developed. Employment of the silane coupling agent, 3-(trimethoxysilyl)propyl methacrylate, enables the incorporation of a high content of LLAZO nanofibers (up to 70 wt%) with the polymer matrix and results in a well-percolated, three-dimensional LLAZO network fully embedded in the PEGDA matrix. Consequently, the silane coupling agent successfully eliminates the agglomeration effect, which ensures higher ionic conductivity, larger lithium transference number, wider electrochemical stability window, and better cycling stability for s@LLZAO-PEGDA CSEs. Excellent cycling stability and extraordinarily high rate capability (up to 10C) are demonstrated in the all-solid-state Li-metal batteries with LiFePO4 and high-voltage Li[Ni1/3Mn1/3Co1/3]O2 cathodes at ambient temperature. This novel design of CSEs with s@LLAZO nanofibers paves the way for a new generation of improved functioning all-solid-state Li-metal batteries.

Research Organization:
West Virginia Univ., Morgantown, WV (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE
Grant/Contract Number:
EE0007806
OSTI ID:
1799379
Alternate ID(s):
OSTI ID: 1601892
Journal Information:
Energy Storage Materials, Vol. 26; ISSN 2405-8297
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 68 works
Citation information provided by
Web of Science

References (50)

Lithium Ion Conducting Poly(ethylene oxide)-Based Solid Electrolytes Containing Active or Passive Ceramic Nanoparticles journal January 2017
Ionic Conductivity and Air Stability of Al-Doped Li 7 La 3 Zr 2 O 12 Sintered in Alumina and Pt Crucibles journal February 2016
Synthesis of Li[sup +] Ion Conductive PEO-PSt Block Copolymer Electrolyte with Microphase Separation Structure journal January 2005
Composite Gel Polymer Electrolyte Based on Poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) with Modified Aluminum-Doped Lithium Lanthanum Titanate (A-LLTO) for High-Performance Lithium Rechargeable Batteries journal August 2016
Li 0.33 La 0.557 TiO 3 ceramic nanofiber-enhanced polyethylene oxide-based composite polymer electrolytes for all-solid-state lithium batteries journal January 2018
Lithium garnets: Synthesis, structure, Li + conductivity, Li + dynamics and applications journal July 2017
Recent advances in all-solid-state rechargeable lithium batteries journal March 2017
Composite solid electrolytes for all-solid-state lithium batteries journal April 2019
PEO/garnet composite electrolytes for solid-state lithium batteries: From “ceramic-in-polymer” to “polymer-in-ceramic” journal April 2018
A lithium superionic conductor journal July 2011
Ionic Conductivity Enhancement of Polymer Electrolytes with Ceramic Nanowire Fillers journal March 2015
Solid-state polymer electrolytes with in-built fast interfacial transport for secondary lithium batteries journal March 2019
Flexible Organic–Inorganic Hybrid Solid Electrolytes Formed via Thiol–Acrylate Photopolymerization journal February 2017
A 3D Nanostructured Hydrogel-Framework-Derived High-Performance Composite Polymer Lithium-Ion Electrolyte journal January 2018
Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries journal October 2017
Trends in polymer electrolytes for secondary lithium batteries journal June 2000
Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries journal June 2016
Complexes of alkali metal ions with poly(ethylene oxide) journal November 1973
Electrochemical performance of a solvent-free hybrid ceramic-polymer electrolyte based on Li 7 La 3 Zr 2 O 12 in P(EO) 15 LiTFSI journal June 2017
Flexible and ion-conducting membrane electrolytes for solid-state lithium batteries: Dispersion of garnet nanoparticles in insulating polyethylene oxide journal October 2016
Effect of Structure on the Fe[sup 3+]∕Fe[sup 2+] Redox Couple in Iron Phosphates journal January 1997
General Observation of Fe 3+ /Fe 2+ Redox Couple Close to 4 V in Partially Substituted Li 2 FeP 2 O 7 Pyrophosphate Solid-Solution Cathodes journal August 2013
Recent progress in polymer materials for advanced lithium-sulfur batteries journal March 2019
Flexible Energy-Storage Devices: Design Consideration and Recent Progress journal June 2014
Synergistic Coupling between Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 and Poly(vinylidene fluoride) Induces High Ionic Conductivity, Mechanical Strength, and Thermal Stability of Solid Composite Electrolytes journal September 2017
Lithium metal anodes for rechargeable batteries journal January 2014
Electrochemical Properties of PEO-Based Polymer Electrolytes Blended with Different Room Temperature Ionic Liquids journal April 2007
Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries journal July 2013
Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface journal April 2017
Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12 journal October 2007
Review—On Order and Disorder in Polymer Electrolytes journal January 2015
Enhancement of ionic conductivity of composite membranes for all-solid-state lithium rechargeable batteries incorporating tetragonal Li7La3Zr2O12 into a polyethylene oxide matrix journal January 2015
Dendrite short-circuit and fuse effect on Li/polymer/Li cells journal July 2006
Synchrotron-radiation XPS analysis of ultra-thin silane films: Specifying the organic silicon journal February 2016
Compatibility of Li[sub 7]La[sub 3]Zr[sub 2]O[sub 12] Solid Electrolyte to All-Solid-State Battery Using Li Metal Anode journal January 2010
Al-incorporation into Li7La3Zr2O12 solid electrolyte keeping stabilized cubic phase for all-solid-state Li batteries journal September 2018
Recent development of sulfide solid electrolytes and interfacial modification for all-solid-state rechargeable lithium batteries journal March 2013
Building better batteries journal February 2008
High-Performance 3-D Fiber Network Composite Electrolyte Enabled with Li-Ion Conducting Nanofibers and Amorphous PEO-Based Cross-Linked Polymer for Ambient All-Solid-State Lithium-Metal Batteries journal July 2019
Chemical versus Electrochemical Electrolyte Oxidation on NMC111, NMC622, NMC811, LNMO, and Conductive Carbon journal September 2017
Steady state current flow in solid binary electrolyte cells journal June 1987
All solid-state polymer electrolytes for high-performance lithium ion batteries journal October 2016
Lithium-ion conductive ceramic textile: A new architecture for flexible solid-state lithium metal batteries journal July 2018
Low Resistance-Integrated All-Solid-State Battery Achieved by Li 7 La 3 Zr 2 O 12 Nanowire Upgrading Polyethylene Oxide (PEO) Composite Electrolyte and PEO Cathode Binder journal October 2018
Garnet-type solid-state fast Li ion conductors for Li batteries: critical review journal January 2014
Recent Progress of the Solid-State Electrolytes for High-Energy Metal-Based Batteries journal January 2018
Oxygen Release and Its Effect on the Cycling Stability of LiNi x Mn y Co z O 2 (NMC) Cathode Materials for Li-Ion Batteries journal January 2017
Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives journal January 2011
Study of the Failure Mechanisms of LiNi 0.8 Mn 0.1 Co 0.1 O 2 Cathode Material for Lithium Ion Batteries journal January 2015
Thin-film lithium and lithium-ion batteries journal November 2000