Exploring the bottlenecks of anionic redox in Li-rich layered sulfides

Saha, Sujoy; Assat, Gaurav; Sougrati, Moulay Tahar; Foix, Dominique; Li, Haifeng; Vergnet, Jean; Turi, Soma; Ha, Yang; Yang, Wanli; Cabana, Jordi; Rousse, Gwenaëlle; Abakumov, Artem M.; Tarascon, Jean-Marie

doi:10.1038/s41560-019-0493-0

Title: Exploring the bottlenecks of anionic redox in Li-rich layered sulfides

Abstract

Anionic redox chemistry has emerged as a new paradigm to design higher-energy lithium ion-battery cathode materials such as Li-rich layered oxides. However, they suffer from voltage fade, large hysteresis and sluggish kinetics, which originate intriguingly from the anionic redox activity itself. To fundamentally understand these issues, we decided to act on the ligand by designing new Li-rich layered sulfides Li_{1.33 – 2y/3}Ti_{0.67 – y/3}FeyS₂, among which the y = 0.3 member shows sustained reversible capacities of ~245 mAh g^-1 due to cumulated cationic (Fe²⁺/³⁺) and anionic (S^2-/S^n-, n < 2) redox processes. Moreover, its negligible initial cycle irreversibility, mitigated voltage fade upon long cycling, low voltage hysteresis and fast kinetics compare positively with its Li-rich oxide analogues. Moving from the oxygen ligand to the sulfur ligand thus partially alleviates the practical bottlenecks affecting anionic redox, although it penalizes the redox potential and energy density. Overall, these sulfides provide chemical clues to improve the holistic performance of anionic redox electrodes, which may guide us to ultimately exploit the energy benefits of oxygen redox.

Authors:

Saha, Sujoy ^[1];

^[1];

^[2]; Foix, Dominique ^[3]; Li, Haifeng ^[4];

^[5]; Turi, Soma ^[6];

^[7];

^[4]; Rousse, Gwenaëlle ^[1]; Abakumov, Artem M. ^[8];

^[1]

Collège de France, Paris (France); Sorbonne Univ., Paris (France); Centre National de la Recherche Scientifique (CNRS), Paris (France)
National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France); ALISTORE-European Research Inst. (France)
National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France)
Univ. of Illinois, Chicago, IL (United States)
Collège de France, Paris (France); Centre National de la Recherche Scientifique (CNRS), Paris (France)
Collège de France, Paris (France)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Skolkovo Inst. of Science and Technology, Moscow (Russia). Center for Energy Science and Technology

Publication Date:: Thu Nov 14 00:00:00 EST 2019

Research Org.:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1594935

Grant/Contract Number:: AC02-05CH11231; AC02- 06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Nature Energy

Additional Journal Information:: Journal Volume: 4; Journal Issue: 11; Journal ID: ISSN 2058-7546

Publisher:: Nature Publishing Group

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Saha, Sujoy, Assat, Gaurav, Sougrati, Moulay Tahar, Foix, Dominique, Li, Haifeng, Vergnet, Jean, Turi, Soma, Ha, Yang, Yang, Wanli, Cabana, Jordi, Rousse, Gwenaëlle, Abakumov, Artem M., and Tarascon, Jean-Marie. Exploring the bottlenecks of anionic redox in Li-rich layered sulfides.  United States: N. p., 2019. 
Web.  doi:10.1038/s41560-019-0493-0.

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                    Saha, Sujoy, Assat, Gaurav, Sougrati, Moulay Tahar, Foix, Dominique, Li, Haifeng, Vergnet, Jean, Turi, Soma, Ha, Yang, Yang, Wanli, Cabana, Jordi, Rousse, Gwenaëlle, Abakumov, Artem M., & Tarascon, Jean-Marie. Exploring the bottlenecks of anionic redox in Li-rich layered sulfides.  United States.  https://doi.org/10.1038/s41560-019-0493-0

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                    Saha, Sujoy, Assat, Gaurav, Sougrati, Moulay Tahar, Foix, Dominique, Li, Haifeng, Vergnet, Jean, Turi, Soma, Ha, Yang, Yang, Wanli, Cabana, Jordi, Rousse, Gwenaëlle, Abakumov, Artem M., and Tarascon, Jean-Marie. Thu .  
"Exploring the bottlenecks of anionic redox in Li-rich layered sulfides".  United States.  https://doi.org/10.1038/s41560-019-0493-0.  https://www.osti.gov/servlets/purl/1594935.

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@article{osti_1594935,

  title        = {Exploring the bottlenecks of anionic redox in Li-rich layered sulfides},

  author       = {Saha, Sujoy and Assat, Gaurav and Sougrati, Moulay Tahar and Foix, Dominique and Li, Haifeng and Vergnet, Jean and Turi, Soma and Ha, Yang and Yang, Wanli and Cabana, Jordi and Rousse, Gwenaëlle and Abakumov, Artem M. and Tarascon, Jean-Marie},

  abstractNote = {Anionic redox chemistry has emerged as a new paradigm to design higher-energy lithium ion-battery cathode materials such as Li-rich layered oxides. However, they suffer from voltage fade, large hysteresis and sluggish kinetics, which originate intriguingly from the anionic redox activity itself. To fundamentally understand these issues, we decided to act on the ligand by designing new Li-rich layered sulfides Li1.33 – 2y/3Ti0.67 – y/3FeyS2, among which the y = 0.3 member shows sustained reversible capacities of ~245 mAh g-1 due to cumulated cationic (Fe2+/3+) and anionic (S2-/Sn-, n < 2) redox processes. Moreover, its negligible initial cycle irreversibility, mitigated voltage fade upon long cycling, low voltage hysteresis and fast kinetics compare positively with its Li-rich oxide analogues. Moving from the oxygen ligand to the sulfur ligand thus partially alleviates the practical bottlenecks affecting anionic redox, although it penalizes the redox potential and energy density. Overall, these sulfides provide chemical clues to improve the holistic performance of anionic redox electrodes, which may guide us to ultimately exploit the energy benefits of oxygen redox.},

  doi          = {10.1038/s41560-019-0493-0},

  journal      = {Nature Energy},

  number       = 11,

  volume       = 4,

  place        = {United States},

  year         = {Thu Nov 14 00:00:00 EST 2019},

  month        = {Thu Nov 14 00:00:00 EST 2019}

}

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Conventional wisdom on utilizing cation redox in intercalation materials for energy storage has been challenged by a new class of cathode materials where oxygen anions actively participate in the reversible electrochemical reaction. This type of Li-rich layered oxides (LRLO) have captured great interests in the field of energy storage materials as they are considered as one of the most promising cathode materials for future high energy density lithium-ion and lithium metal batteries. However, the activation of solid-state oxygen redox reaction usually causes some detrimental effects on the electrochemical performance (e.g., O₂ loss, voltage fade) preventing the practical application of LRLOmore »« less
https://doi.org/10.2172/1770710

Full Text Available
Structure and Voltage Recovery Driven by Defects Elimination in Li-Rich Layered Oxide Cathode Materials

Conference Zhang, Minghao ; Liu, Haodong ; Meng, Ying Shirley

Lithium-ion batteries (LIBs) are ubiquitous in a wide range of technologies, including cell phones, electric vehicles, and energy grid, and are indispensable in the transition toward sustainable energy technology. The battery performance is inherently connected to the capability of lithium ions to reversibly intercalate with the electrodes. The capacity of classical layered transition metal (TM) oxides, the primary commercial cathode materials, is limited to cationic redox activity. Anionic redox has thus emerged as a new paradigm for designing novel cathodes for next generation LIBs. It is recently confirmed oxygen redox in lithium-rich layered oxides (LRLO) with composition xLi₂MnO₃∙(1-x)LiTMO₂, which enablesmore »« less
https://doi.org/10.2172/1770702

Full Text Available

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Title: Exploring the bottlenecks of anionic redox in Li-rich layered sulfides

Abstract

Citation Formats

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes journal, July 2013

Generalized Gradient Approximation Made Simple journal, October 1996

Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries journal, January 2001

Influence of the cation nature of high sulfur content oxysulfide thin films MO S (M=W, Ti) studied by XPS journal, September 2004

Performance and cost of materials for lithium-based rechargeable automotive batteries journal, April 2018

Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3 journal, February 2017

Lithium Batteries and Cathode Materials journal, October 2004

The Role of Oxygen Release from Li- and Mn-Rich Layered Oxides during the First Cycles Investigated by On-Line Electrochemical Mass Spectrometry journal, December 2016

Tracking the Chemical and Structural Evolution of the TiS 2 Electrode in the Lithium-Ion Cell Using Operando X-ray Absorption Spectroscopy journal, June 2018

Quantitative Analysis of the Initial Restructuring Step of Nanostructured FeSn 2 -Based Anodes for Li-Ion Batteries journal, June 2013

Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials journal, April 2018

Redox processes in the LixFeS2/Li electrochemical system studied through crystal, Mössbauer, and EXAFS analyses journal, May 1989

Li(V0.5Ti0.5)S2 as a 1 V lithium intercalation electrode journal, March 2016

Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering journal, June 2018

Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries journal, January 2017

Polarized X-ray absorption spectroscopy and XPS of TiS3: S K- and Ti L-edge XANES and S and Ti 2p XPS journal, June 2005

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Electrochemical characteristics of transition-metal trichalcogenides in the secondary lithium battery journal, November 1983

Thermodynamic Activation of Charge Transfer in Anionic Redox Process for Li-Ion Batteries journal, November 2017

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal, January 1998

Evolution of local electronic structure in alabandite and niningerite solid solutions [(Mn,Fe)S, (Mg,Mn)S, (Mg,Fe)S] using sulfur K - and L -edge XANES spectroscopy journal, October 2002

Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide journal, June 2015

Transition metal sulfides as cathodes for secondary lithium batteries—II. titanium sulfides journal, June 1977

A Reversible Rocksalt to Amorphous Phase Transition Involving Anion Redox journal, October 2018

Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes journal, December 2017

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries journal, January 2016

The Role of Ternary Phases in Cathode Reactions journal, January 1976

The Electrochemical Sodiation of FeSb 2 : New Insights from Operando 57 Fe Synchrotron Mössbauer and X-Ray Absorption Spectroscopy journal, October 2018

High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source journal, March 2017

Locating redox couples in the layered sulfides with application to Cu[Cr2]S4 journal, October 2009

Mössbauer studies of some sulphide minerals journal, March 1971

Approaching the limits of cationic and anionic electrochemical activity with the Li-rich layered rocksalt Li3IrO4 journal, December 2017

Transition-metal dichalcogenides from disintercalation processes. Crystal structure determination and Mossbauer study of Li 2 FeS 2 and its disintercalates Li x FeS 2 (0.2⩽x⩽2) journal, September 1987

Effect of the damping function in dispersion corrected density functional theory journal, March 2011

On the Crystal Structures of TiS3, ZrS3, ZrSe3, ZrTe3, HfS3, and HfSe3. journal, January 1975

Metal chalcogenides as reversible electrodes in nonaqueous lithium batteries journal, July 1977

Understanding the Anomalous Capacity of Li / Li [ NixLi ( 1 / 3 − 2x / 3 ) Mn ( 2 / 3 − x / 3 ) ] O2 Cells Using In Situ X-Ray Diffraction and Electrochemical Studies journal, January 2002

Anionic Redox in Rechargeable Lithium Batteries journal, June 2017

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen journal, March 2016

Chemistry of intercalation compounds: Metal guests in chalcogenide hosts journal, January 1978

The Development and Future of Lithium Ion Batteries journal, December 2016

Preparation and chemical and physical properties of the new layered phases Li x Ti 1 − y M y S 2 with M = V , C r , o r F e journal, December 1983

Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox journal, January 2018

Synthesis, Structure, and Electrochemical Behavior of Li[Ni[sub x]Li[sub 1/3−2x/3]Mn[sub 2/3−x/3]]O[sub 2] journal, January 2002

The Chemistry of TiS[sub 3] and NbSe[sub 3] Cathodes journal, January 1976

Electrical Energy Storage and Intercalation Chemistry journal, June 1976

High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold journal, June 1972

Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries journal, April 2018

Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV journal, January 1976

XPS investigations of TiOySz amorphous thin films used as positive electrode in lithium microbatteries journal, May 2005

Anion–Cation Redox Competition and the Formation of New Compounds in Highly Covalent Systems journal, September 1996

Indexing of powder diffraction patterns for low-symmetry lattices by the successive dichotomy method journal, December 1991

Mössbauer 57Fe spectra exhibiting “ferrous character” journal, July 1980

Antisite occupation induced single anionic redox chemistry and structural stabilization of layered sodium chromium sulfide journal, September 2017

Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis journal, February 2013

Xanes Spectroscopy of Sulfur in Earth Materials journal, December 2005

Lithium Batteries and Cathode Materials journal, December 2004

Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction journal, April 2020

Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal, May 2021

The Electrochemical Sodiation of FeSb 2 : New Insights from Operando 57 Fe Synchrotron Mössbauer and X-Ray Absorption Spectroscopy journal, January 2019

Anion–Cation Redox Competition and the Formation of New Compounds in Highly Covalent Systems journal, September 1996

Quantitative Analysis of the Initial Restructuring Step of Nanostructured FeSn 2 -Based Anodes for Li-Ion Batteries journal, June 2013

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes journal, July 2013

Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries journal, April 2018

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries journal, April 2017

On the Crystal Structures of TiS3, ZrS3, ZrSe3, ZrTe3, HfS3, and HfSe3. journal, January 1975

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013

Generalized Gradient Approximation Made Simple
journal, October 1996

Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries
journal, January 2001

Influence of the cation nature of high sulfur content oxysulfide thin films MO S (M=W, Ti) studied by XPS
journal, September 2004

Performance and cost of materials for lithium-based rechargeable automotive batteries
journal, April 2018

Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3
journal, February 2017

Lithium Batteries and Cathode Materials
journal, October 2004

The Role of Oxygen Release from Li- and Mn-Rich Layered Oxides during the First Cycles Investigated by On-Line Electrochemical Mass Spectrometry
journal, December 2016

Tracking the Chemical and Structural Evolution of the TiS ₂ Electrode in the Lithium-Ion Cell Using Operando X-ray Absorption Spectroscopy
journal, June 2018

Quantitative Analysis of the Initial Restructuring Step of Nanostructured FeSn ₂ -Based Anodes for Li-Ion Batteries
journal, June 2013

Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials
journal, April 2018

Redox processes in the LixFeS2/Li electrochemical system studied through crystal, Mössbauer, and EXAFS analyses
journal, May 1989

Li(V0.5Ti0.5)S2 as a 1 V lithium intercalation electrode
journal, March 2016

Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering
journal, June 2018

Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries
journal, January 2017

Polarized X-ray absorption spectroscopy and XPS of TiS3: S K- and Ti L-edge XANES and S and Ti 2p XPS
journal, June 2005

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Electrochemical characteristics of transition-metal trichalcogenides in the secondary lithium battery
journal, November 1983

Thermodynamic Activation of Charge Transfer in Anionic Redox Process for Li-Ion Batteries
journal, November 2017

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

Evolution of local electronic structure in alabandite and niningerite solid solutions [(Mn,Fe)S, (Mg,Mn)S, (Mg,Fe)S] using sulfur K - and L -edge XANES spectroscopy
journal, October 2002

Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide
journal, June 2015

Transition metal sulfides as cathodes for secondary lithium batteries—II. titanium sulfides
journal, June 1977

A Reversible Rocksalt to Amorphous Phase Transition Involving Anion Redox
journal, October 2018

Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes
journal, December 2017

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries
journal, January 2016

The Role of Ternary Phases in Cathode Reactions
journal, January 1976

The Electrochemical Sodiation of FeSb ₂ : New Insights from Operando ⁵⁷ Fe Synchrotron Mössbauer and X-Ray Absorption Spectroscopy
journal, October 2018

High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source
journal, March 2017

Locating redox couples in the layered sulfides with application to Cu[Cr2]S4
journal, October 2009

Mössbauer studies of some sulphide minerals
journal, March 1971

Approaching the limits of cationic and anionic electrochemical activity with the Li-rich layered rocksalt Li3IrO4
journal, December 2017

Transition-metal dichalcogenides from disintercalation processes. Crystal structure determination and Mossbauer study of Li ₂ FeS ₂ and its disintercalates Li _x FeS ₂ (0.2⩽x⩽2)
journal, September 1987

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

On the Crystal Structures of TiS3, ZrS3, ZrSe3, ZrTe3, HfS3, and HfSe3.
journal, January 1975

Metal chalcogenides as reversible electrodes in nonaqueous lithium batteries
journal, July 1977

Understanding the Anomalous Capacity of Li / Li [ Ni_xLi _{( 1 / 3 − 2x / 3 )} Mn_{( 2 / 3 − x / 3 )} ] O₂ Cells Using In Situ X-Ray Diffraction and Electrochemical Studies
journal, January 2002

Anionic Redox in Rechargeable Lithium Batteries
journal, June 2017

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016

Chemistry of intercalation compounds: Metal guests in chalcogenide hosts
journal, January 1978

The Development and Future of Lithium Ion Batteries
journal, December 2016

Preparation and chemical and physical properties of the new layered phases ${Li}_{x} {Ti}_{1 - y} M_{y} S_{2}$ with $M = V, C r, o r F e$
journal, December 1983

Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox
journal, January 2018

Synthesis, Structure, and Electrochemical Behavior of Li[Ni[sub x]Li[sub 1/3−2x/3]Mn[sub 2/3−x/3]]O[sub 2]
journal, January 2002

The Chemistry of TiS[sub 3] and NbSe[sub 3] Cathodes
journal, January 1976

Electrical Energy Storage and Intercalation Chemistry
journal, June 1976

High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold
journal, June 1972

Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries
journal, April 2018

Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV
journal, January 1976

XPS investigations of TiOySz amorphous thin films used as positive electrode in lithium microbatteries
journal, May 2005

Anion–Cation Redox Competition and the Formation of New Compounds in Highly Covalent Systems
journal, September 1996

Indexing of powder diffraction patterns for low-symmetry lattices by the successive dichotomy method
journal, December 1991

Mössbauer 57Fe spectra exhibiting “ferrous character”
journal, July 1980

Antisite occupation induced single anionic redox chemistry and structural stabilization of layered sodium chromium sulfide
journal, September 2017

Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
journal, February 2013

Xanes Spectroscopy of Sulfur in Earth Materials
journal, December 2005

Lithium Batteries and Cathode Materials
journal, December 2004

Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020

Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021

The Electrochemical Sodiation of FeSb ₂ : New Insights from Operando ⁵⁷ Fe Synchrotron Mössbauer and X-Ray Absorption Spectroscopy
journal, January 2019

Anion–Cation Redox Competition and the Formation of New Compounds in Highly Covalent Systems
journal, September 1996

Quantitative Analysis of the Initial Restructuring Step of Nanostructured FeSn ₂ -Based Anodes for Li-Ion Batteries
journal, June 2013

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013

Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries
journal, April 2018

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries
journal, April 2017

On the Crystal Structures of TiS3, ZrS3, ZrSe3, ZrTe3, HfS3, and HfSe3.
journal, January 1975