Role of Dynamically Frustrated Bond Disorder in a Li+ Superionic Solid Electrolyte

Adelstein, Nicole; Wood, Brandon C.

doi:10.1021/acs.chemmater.6b00790

Title: Role of Dynamically Frustrated Bond Disorder in a Li⁺ Superionic Solid Electrolyte

Abstract

Inorganic lithium solid electrolytes are critical components in next-generation solid-state batteries, yet the fundamental nature of the cation-anion interactions and their relevance for ionic conductivity in these materials remains enigmatic. Here, we employ first-principles molecular dynamics simulations to explore the interplay between chemistry, structure, and functionality of a highly conductive Li⁺ solid electrolyte, Li3InBr6. Using local-orbital projections to dynamically track the evolution of the electronic charge density, the simulations reveal rapid, correlated fluctuations between cation-anion interactions with different degrees of directional covalent character. These chemical bond dynamics are shown to correlate with Li⁺ mobility, and are enabled thermally by intrinsic frustration between the preferred geometries of chemical bonding and lattice symmetry. We suggest that the fluctuating chemical environment from the polarizable anions functions similar to a solvent, contributing to the superionic behavior of Li₃InBr₆ by temporarily stabilizing configurations favorable for migrating Li⁺. The generality of these conclusions for understanding solid electrolytes and key factors governing the superionic phase transition is discussed.

Authors:

Adelstein, Nicole ^[1]; Wood, Brandon C. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Publication Date:: Fri Sep 16 00:00:00 EDT 2016

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1408073

Report Number(s):: LLNL-JRNL-684599
Journal ID: ISSN 0897-4756; TRN: US1702929

Grant/Contract Number:: AC52-07NA27344

Resource Type:: Accepted Manuscript

Journal Name:: Chemistry of Materials

Additional Journal Information:: Journal Volume: 28; Journal Issue: 20; Journal ID: ISSN 0897-4756

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 25 ENERGY STORAGE

Citation Formats


                    Adelstein, Nicole, and Wood, Brandon C. Role of Dynamically Frustrated Bond Disorder in a Li+ Superionic Solid Electrolyte.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.chemmater.6b00790.

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                    Adelstein, Nicole, & Wood, Brandon C. Role of Dynamically Frustrated Bond Disorder in a Li+ Superionic Solid Electrolyte.  United States.  https://doi.org/10.1021/acs.chemmater.6b00790

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                    Adelstein, Nicole, and Wood, Brandon C. Fri .  
"Role of Dynamically Frustrated Bond Disorder in a Li+ Superionic Solid Electrolyte".  United States.  https://doi.org/10.1021/acs.chemmater.6b00790.  https://www.osti.gov/servlets/purl/1408073.

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@article{osti_1408073,

  title        = {Role of Dynamically Frustrated Bond Disorder in a Li+ Superionic Solid Electrolyte},

  author       = {Adelstein, Nicole and Wood, Brandon C.},

  abstractNote = {Inorganic lithium solid electrolytes are critical components in next-generation solid-state batteries, yet the fundamental nature of the cation-anion interactions and their relevance for ionic conductivity in these materials remains enigmatic. Here, we employ first-principles molecular dynamics simulations to explore the interplay between chemistry, structure, and functionality of a highly conductive Li+ solid electrolyte, Li3InBr6. Using local-orbital projections to dynamically track the evolution of the electronic charge density, the simulations reveal rapid, correlated fluctuations between cation-anion interactions with different degrees of directional covalent character. These chemical bond dynamics are shown to correlate with Li+ mobility, and are enabled thermally by intrinsic frustration between the preferred geometries of chemical bonding and lattice symmetry. We suggest that the fluctuating chemical environment from the polarizable anions functions similar to a solvent, contributing to the superionic behavior of Li3InBr6 by temporarily stabilizing configurations favorable for migrating Li+. The generality of these conclusions for understanding solid electrolytes and key factors governing the superionic phase transition is discussed.},

  doi          = {10.1021/acs.chemmater.6b00790},

  journal      = {Chemistry of Materials},

  number       = 20,

  volume       = 28,

  place        = {United States},

  year         = {Fri Sep 16 00:00:00 EDT 2016},

  month        = {Fri Sep 16 00:00:00 EDT 2016}

}

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Title: Role of Dynamically Frustrated Bond Disorder in a Li+ Superionic Solid Electrolyte

Abstract

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Inorganic solid Li ion conductors: An overview journal, June 2009

Mechanisms of Li + transport in garnet-type cubic Li 3 + x La 3 M 2 O 12 ( M = Te, Nb, Zr) journal, February 2012

Lithium Lanthanum Titanium Oxides: A Fast Ionic Conductive Coating for Lithium-Ion Battery Cathodes journal, July 2012

First Principles Study of the Li10GeP2S12 Lithium Super Ionic Conductor Material journal, December 2011

The effects of counter cation on lithium ion conductivity: In the case of the perovskite-type titanium oxides of La2/3−x Li3xTiO3 and LaTiO3 journal, May 2009

Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte journal, October 2015

Dynamics of Coupled Lithium/Electron Diffusion in TiO 2 Polymorphs journal, November 2009

Concerted Migration Mechanism in the Li Ion Dynamics of Garnet-Type Li 7 La 3 Zr 2 O 12 journal, January 2013

Informatics-Aided Density Functional Theory Study on the Li Ion Transport of Tavorite-Type LiMTO 4 F (M 3+ –T 5+ , M 2+ –T 6+ ) journal, May 2015

Visualizing Lithium-Ion Migration Pathways in Battery Materials journal, October 2013

Structural and Mechanistic Insights into Fast Lithium-Ion Conduction in Li 4 SiO 4 –Li 3 PO 4 Solid Electrolytes journal, July 2015

Structural requirements for fast lithium ion migration in Li10GeP2S12 journal, January 2012

Design principles for solid-state lithium superionic conductors journal, August 2015

Phase Stability and Transport Mechanisms in Antiperovskite Li 3 OCl and Li 3 OBr Superionic Conductors journal, November 2013

High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory journal, September 2015

Role of Na + Interstitials and Dopants in Enhancing the Na + Conductivity of the Cubic Na 3 PS 4 Superionic Conductor journal, December 2015

Insights into the Performance Limits of the Li 7 P 3 S 11 Superionic Conductor: A Combined First-Principles and Experimental Study journal, March 2016

Structural Principles of α ‐ AgI and Related Double Salts journal, June 1976

A chemical approach for the microscopic mechanism of fast ion transport in solids journal, January 1992

Superionicity as a local fluctuation of the chemical bond journal, May 1994

Coupled motions of ions and electrons in some superionic conductors: An ab initio molecular dynamics study journal, October 2006

Microscopic study of superionic transition journal, February 1996

Dynamical Structure, Bonding, and Thermodynamics of the Superionic Sublattice in α − AgI journal, October 2006

Superionics: crystal structures and conduction processes journal, June 2004

Diffusion of Mobile Ions and Bond Fluctuations in Superionic Conductor CuI from ab initio Molecular-Dynamics Simulations journal, November 2003

Relationships between Atomic Diffusion Mechanisms and Ensemble Transport Coefficients in Crystalline Polymorphs journal, April 2014

Diffusion within α-CuI studied using ab initio molecular dynamics simulations journal, July 2009

Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction journal, December 2015

The crystallography of correlated disorder journal, May 2015

New Lithium Ion Conductor Li 3 InBr 6 Studied by 7 Li NMR journal, March 1998

Lithium superionic conductors Li3InBr6 and LiInBr4 studied by 7Li, 115In NMR journal, October 2006

Zur Kristallstruktur von Li3InCl6 journal, April 1999

Structure and Ionic Conductivity of Halocomplexes of Main Group Metallic Elements Studied by NMR and NQR journal, November 2005

Unified Approach for Molecular Dynamics and Density-Functional Theory journal, November 1985

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials journal, September 2009

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism journal, April 1990

Generalized Gradient Approximation Made Simple journal, October 1996

Nosé–Hoover chains: The canonical ensemble via continuous dynamics journal, August 1992

Maximally localized Wannier functions: Theory and applications journal, October 2012

Resolving the hydrogen bond dynamics conundrum journal, December 2000

Sparse Cyclic Excitations Explain the Low Ionic Conductivity of Stoichiometric Li 7 La 3 Zr 2 O 12 journal, March 2016

Migration barriers for cations and anions in alkali halide crystals journal, July 1959

High-Pressure-High-Temperature Study of Spin-Lattice Relaxation in Pure and Doped LiBr Single Crystals journal, January 1970

Fast Ionic Conductivity and Dielectric Properties of the Lithium Halide Spinels Li2MnCl4, Li2CdCl4, Li2MnBr4, and Li2CdBr4 journal, August 1984

Conductivity enhancement of lithium bromide monohydrate by Al2O3 particles journal, September 1982

Fast lithium-ion transport in composites containing lithium-bromide dihydrate journal, September 1982

Investigation of ionic transport in composites by nuclear magnetic resonance journal, November 1991

Enhanced ionic conductivity in nano-composite solid polymer electrolyte: (PEG) x LiBr: y(SiO2) journal, September 2010

Substitution effect of ionic conductivity in lithium ion conductor, LI3INBR6−xCLx journal, September 2008

Substitution Effect for Br on the Lithium Ion Conductivity of Lithium Indium Bromide journal, August 2009

Li + Cation Environment, Transport, and Mechanical Properties of the LiTFSI Doped N -Methyl- N -alkylpyrrolidinium + TFSI - Ionic Liquids journal, August 2006

Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations journal, September 2006

Breakdown of absolute rate theory and prefactor anomalies in superionic conductors journal, March 1978

Effect of low dimensionality on prefactor anomalies in superionic conductors journal, March 1978

The universal low frequency responses of ionic conductors: A review of data and a unified model interpretation journal, October 1981

Anisotropic conductivity in a channel-structured superionic conductor: Li2Ti3O7 journal, September 1979

High pressure NMR study of the prefactor anomaly in the lithium intercalation compound Li0.94TiS2 journal, June 1981

Simulation of prefactor anomalies in superionic conductors in the case of arbitrary energy losses journal, February 2008

Structure and Dynamics of Li3InBr6 and NaInBr4 by Means of Nuclear Magnetic Resonance journal, January 1998

Ordering of the silver ions in α-AgI: A mechanism for the α-β phase transition journal, May 1992

From order to disorder: The structure of lithium-conducting garnets Li7−xLa3TaxZr2−xO12 (x=0–2) journal, January 2012

Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte journal, September 2019

Lithium Chlorides and Bromides as Promising Solid‐State Chemistries for Fast Ion Conductors with Good Electrochemical Stability journal, June 2019

Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte journal, November 2019

Ab initio simulations of liquid electrolytes for energy conversion and storage journal, October 2018

High-throughput computational screening for solid-state Li-ion conductors journal, January 2020

Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries journal, April 2018

Lithium diffusion in L i 2 X ( X = O , S, and Se): Ab initio simulations and inelastic neutron scattering measurements journal, June 2019

Reorientational motion and Li + -ion transport in Li 2 B 12 H 12 system: Molecular dynamics study journal, July 2019

Lithium Chlorides and Bromides as Promising Solid‐State Chemistries for Fast Ion Conductors with Good Electrochemical Stability journal, May 2019

High-throughput computational screening for solid-state Li-ion conductors text, January 2019

Title: Role of Dynamically Frustrated Bond Disorder in a Li⁺ Superionic Solid Electrolyte

Inorganic solid Li ion conductors: An overview
journal, June 2009

Mechanisms of Li $^{+}$ transport in garnet-type cubic Li $_{3 + x}$ La $_{3} M_{2}$ O $_{12}$ ( $M$ = Te, Nb, Zr)
journal, February 2012

Lithium Lanthanum Titanium Oxides: A Fast Ionic Conductive Coating for Lithium-Ion Battery Cathodes
journal, July 2012

First Principles Study of the Li₁₀GeP₂S₁₂ Lithium Super Ionic Conductor Material
journal, December 2011

The effects of counter cation on lithium ion conductivity: In the case of the perovskite-type titanium oxides of La2/3−x Li3xTiO3 and LaTiO3
journal, May 2009

Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte
journal, October 2015

Dynamics of Coupled Lithium/Electron Diffusion in TiO ₂ Polymorphs
journal, November 2009

Concerted Migration Mechanism in the Li Ion Dynamics of Garnet-Type Li ₇ La ₃ Zr ₂ O ₁₂
journal, January 2013

Informatics-Aided Density Functional Theory Study on the Li Ion Transport of Tavorite-Type LiMTO 4 F (M 3+ –T 5+ , M 2+ –T 6+ )
journal, May 2015

Visualizing Lithium-Ion Migration Pathways in Battery Materials
journal, October 2013

Structural and Mechanistic Insights into Fast Lithium-Ion Conduction in Li ₄ SiO ₄ –Li ₃ PO ₄ Solid Electrolytes
journal, July 2015

Structural requirements for fast lithium ion migration in Li10GeP2S12
journal, January 2012

Design principles for solid-state lithium superionic conductors
journal, August 2015

Phase Stability and Transport Mechanisms in Antiperovskite Li ₃ OCl and Li ₃ OBr Superionic Conductors
journal, November 2013

High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory
journal, September 2015

Role of Na ⁺ Interstitials and Dopants in Enhancing the Na ⁺ Conductivity of the Cubic Na ₃ PS ₄ Superionic Conductor
journal, December 2015

Insights into the Performance Limits of the Li ₇ P ₃ S ₁₁ Superionic Conductor: A Combined First-Principles and Experimental Study
journal, March 2016

Structural Principles of α ‐ AgI and Related Double Salts
journal, June 1976

A chemical approach for the microscopic mechanism of fast ion transport in solids
journal, January 1992

Superionicity as a local fluctuation of the chemical bond
journal, May 1994

Coupled motions of ions and electrons in some superionic conductors: An ab initio molecular dynamics study
journal, October 2006

Microscopic study of superionic transition
journal, February 1996

Dynamical Structure, Bonding, and Thermodynamics of the Superionic Sublattice in $α − AgI$
journal, October 2006

Superionics: crystal structures and conduction processes
journal, June 2004

Diffusion of Mobile Ions and Bond Fluctuations in Superionic Conductor CuI from ab initio Molecular-Dynamics Simulations
journal, November 2003

Relationships between Atomic Diffusion Mechanisms and Ensemble Transport Coefficients in Crystalline Polymorphs
journal, April 2014

Diffusion within α-CuI studied using ab initio molecular dynamics simulations
journal, July 2009

Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction
journal, December 2015

The crystallography of correlated disorder
journal, May 2015

New Lithium Ion Conductor Li ₃ InBr ₆ Studied by ⁷ Li NMR
journal, March 1998

Lithium superionic conductors Li3InBr6 and LiInBr4 studied by 7Li, 115In NMR
journal, October 2006

Zur Kristallstruktur von Li3InCl6
journal, April 1999

Structure and Ionic Conductivity of Halocomplexes of Main Group Metallic Elements Studied by NMR and NQR
journal, November 2005

Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990

Generalized Gradient Approximation Made Simple
journal, October 1996

Nosé–Hoover chains: The canonical ensemble via continuous dynamics
journal, August 1992

Maximally localized Wannier functions: Theory and applications
journal, October 2012

Resolving the hydrogen bond dynamics conundrum
journal, December 2000

Sparse Cyclic Excitations Explain the Low Ionic Conductivity of Stoichiometric ${Li}_{7} {La}_{3} {Zr}_{2} O_{12}$
journal, March 2016

Migration barriers for cations and anions in alkali halide crystals
journal, July 1959

High-Pressure-High-Temperature Study of Spin-Lattice Relaxation in Pure and Doped LiBr Single Crystals
journal, January 1970

Fast Ionic Conductivity and Dielectric Properties of the Lithium Halide Spinels Li2MnCl4, Li2CdCl4, Li2MnBr4, and Li2CdBr4
journal, August 1984

Conductivity enhancement of lithium bromide monohydrate by Al2O3 particles
journal, September 1982

Fast lithium-ion transport in composites containing lithium-bromide dihydrate
journal, September 1982

Investigation of ionic transport in composites by nuclear magnetic resonance
journal, November 1991

Enhanced ionic conductivity in nano-composite solid polymer electrolyte: (PEG) x LiBr: y(SiO2)
journal, September 2010

Substitution effect of ionic conductivity in lithium ion conductor, LI3INBR6−xCLx
journal, September 2008

Substitution Effect for Br on the Lithium Ion Conductivity of Lithium Indium Bromide
journal, August 2009

Li ⁺ Cation Environment, Transport, and Mechanical Properties of the LiTFSI Doped N -Methyl- N -alkylpyrrolidinium ⁺ TFSI ^- Ionic Liquids
journal, August 2006

Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations
journal, September 2006

Breakdown of absolute rate theory and prefactor anomalies in superionic conductors
journal, March 1978

Effect of low dimensionality on prefactor anomalies in superionic conductors
journal, March 1978

The universal low frequency responses of ionic conductors: A review of data and a unified model interpretation
journal, October 1981

Anisotropic conductivity in a channel-structured superionic conductor: Li2Ti3O7
journal, September 1979

High pressure NMR study of the prefactor anomaly in the lithium intercalation compound Li0.94TiS2
journal, June 1981

Simulation of prefactor anomalies in superionic conductors in the case of arbitrary energy losses
journal, February 2008

Structure and Dynamics of Li3InBr6 and NaInBr4 by Means of Nuclear Magnetic Resonance
journal, January 1998

Ordering of the silver ions in α-AgI: A mechanism for the α-β phase transition
journal, May 1992

From order to disorder: The structure of lithium-conducting garnets Li7−xLa3TaxZr2−xO12 (x=0–2)
journal, January 2012

Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte
journal, September 2019

Lithium Chlorides and Bromides as Promising Solid‐State Chemistries for Fast Ion Conductors with Good Electrochemical Stability
journal, June 2019

Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte
journal, November 2019

Ab initio simulations of liquid electrolytes for energy conversion and storage
journal, October 2018

High-throughput computational screening for solid-state Li-ion conductors
journal, January 2020

Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries
journal, April 2018

Lithium diffusion in $L i_{2} X$ ( $X = O$ , S, and Se): Ab initio simulations and inelastic neutron scattering measurements
journal, June 2019

Reorientational motion and ${Li}^{+}$ -ion transport in ${Li}_{2} B_{12} H_{12}$ system: Molecular dynamics study
journal, July 2019

Lithium Chlorides and Bromides as Promising Solid‐State Chemistries for Fast Ion Conductors with Good Electrochemical Stability
journal, May 2019

High-throughput computational screening for solid-state Li-ion conductors
text, January 2019