Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries

Nagarajan, Sudhan; Hwang, Sooyeon; Balasubramanian, Mahalingam; Thangavel, Naresh Kumar; Arava, Leela Mohana Reddy

doi:10.1021/jacs.1c06828

Title: Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries

Abstract

Mixed cationic and anionic redox cathode chemistry is emerging as conventional cationic-redox of transition metal based layered oxides are reaching their theoretical capacity limit. However, these anionic redox in transition metal oxide-based cathodes attained by taking excess lithium has resulted in stability issues due to weak metal - oxygen ligand covalency. Here, we present an alternative approach of improving metal - ligand covalency by introducing less electronegative chalcogen ligand (sulfur) in the cathode structural framework where the metal dband penetration into ligand p-band thereby utilizing reversible mixed anionic and cationic redox chemistry. Through this design strategy, we report possibility of developing a new family of layered cathode materials when partially filled d orbital redox couples like Fe^2+/3+ are introduced in the Li-ion conducting phase (Li₂SnS₃). Further, the electron energy loss spectroscopy (EELS) and X-ray absorption near-edge structure (XANES) analysis are used to qualitatively identify the charge contributors at the metal and ligand sites during Li⁺ extraction. The detailed high-resolution transmission electron microscopy (HR-TEM) and high annular dark field-scanning transmission electron microscopy (HAADF-STEM) investigation reveal the multi redox induced structural modifications and its surface amorphization with nanopore formation during cycling. Findings from this study will shed light on designing Ni andmore »« less

Authors:

Nagarajan, Sudhan ^[1];

^[2]; Balasubramanian, Mahalingam ^[3];

^[1];

^[1]

Wayne State Univ., Detroit, MI (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Publication Date:: Wed Sep 15 00:00:00 EDT 2021

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

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

OSTI Identifier:: 1825730

Alternate Identifier(s):: OSTI ID: 1854353

Report Number(s):: BNL-222235-2021-JAAM
Journal ID: ISSN 0002-7863

Grant/Contract Number:: SC0012704; AC02-06CH11357; 2127519

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 143; Journal Issue: 38; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; Sulfide cathode; Anionic and Cationic redox; Chalcogen cathode; HAADF-STEM; Cathode materials

Citation Formats


                    Nagarajan, Sudhan, Hwang, Sooyeon, Balasubramanian, Mahalingam, Thangavel, Naresh Kumar, and Arava, Leela Mohana Reddy. Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries.  United States: N. p., 2021. 
Web.  doi:10.1021/jacs.1c06828.

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                    Nagarajan, Sudhan, Hwang, Sooyeon, Balasubramanian, Mahalingam, Thangavel, Naresh Kumar, & Arava, Leela Mohana Reddy. Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries.  United States.  https://doi.org/10.1021/jacs.1c06828

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                    Nagarajan, Sudhan, Hwang, Sooyeon, Balasubramanian, Mahalingam, Thangavel, Naresh Kumar, and Arava, Leela Mohana Reddy. Wed .  
"Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries".  United States.  https://doi.org/10.1021/jacs.1c06828.  https://www.osti.gov/servlets/purl/1825730.

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@article{osti_1825730,

  title        = {Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries},

  author       = {Nagarajan, Sudhan and Hwang, Sooyeon and Balasubramanian, Mahalingam and Thangavel, Naresh Kumar and Arava, Leela Mohana Reddy},

  abstractNote = {Mixed cationic and anionic redox cathode chemistry is emerging as conventional cationic-redox of transition metal based layered oxides are reaching their theoretical capacity limit. However, these anionic redox in transition metal oxide-based cathodes attained by taking excess lithium has resulted in stability issues due to weak metal - oxygen ligand covalency. Here, we present an alternative approach of improving metal - ligand covalency by introducing less electronegative chalcogen ligand (sulfur) in the cathode structural framework where the metal dband penetration into ligand p-band thereby utilizing reversible mixed anionic and cationic redox chemistry. Through this design strategy, we report possibility of developing a new family of layered cathode materials when partially filled d orbital redox couples like Fe2+/3+ are introduced in the Li-ion conducting phase (Li2SnS3). Further, the electron energy loss spectroscopy (EELS) and X-ray absorption near-edge structure (XANES) analysis are used to qualitatively identify the charge contributors at the metal and ligand sites during Li+ extraction. The detailed high-resolution transmission electron microscopy (HR-TEM) and high annular dark field-scanning transmission electron microscopy (HAADF-STEM) investigation reveal the multi redox induced structural modifications and its surface amorphization with nanopore formation during cycling. Findings from this study will shed light on designing Ni and Co free chalcogen cathodes and various functional materials in the chalcogen based dual anionic and cationic redox cathode avenue.},

  doi          = {10.1021/jacs.1c06828},

  journal      = {Journal of the American Chemical Society},

  number       = 38,

  volume       = 143,

  place        = {United States},

  year         = {Wed Sep 15 00:00:00 EDT 2021},

  month        = {Wed Sep 15 00:00:00 EDT 2021}

}

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Title: Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries

Abstract

Citation Formats

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

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal, June 2005

Challenges for Rechargeable Li Batteries journal, February 2010

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Lithium Batteries and Cathode Materials journal, October 2004

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

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

Understanding the Roles of Anionic Redox and Oxygen Release during Electrochemical Cycling of Lithium-Rich Layered Li 4 FeSbO 6 journal, April 2015

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Li 2 FeS 2 , a cathodic material for lithium secondary battery journal, October 1981

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

Lithium-rich layered titanium sulfides: Cobalt- and Nickel-free high capacity cathode materials for lithium-ion batteries journal, April 2020

Elucidation of Active Oxygen Sites upon Delithiation of Li 3 IrO 4 journal, December 2020

Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries journal, June 2019

Extended Interfacial Stability through Simple Acid Rinsing in a Li-Rich Oxide Cathode Material journal, April 2020

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

Atomic-Scale Investigation of Defects, Dopants, and Lithium Transport in the LiFePO 4 Olivine-Type Battery Material journal, October 2005

First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk journal, September 2020

Review of the U.S. Department of Energy’s “Deep Dive” Effort to Understand Voltage Fade in Li- and Mn-Rich Cathodes journal, October 2015

The Role of Intragranular Nanopores in Capacity Fade of Nickel-Rich Layered Li(Ni 1– x – y Co x Mn y )O 2 Cathode Materials journal, August 2019

Lithium iron thio-phosphate: a new 3 V sulfide cathode journal, April 2003

Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release journal, July 2018

Fast Lithium Ion Conduction in Li 2 SnS 3 : Synthesis, Physicochemical Characterization, and Electronic Structure journal, December 2014

Monodisperse Porous LiFePO 4 Microspheres for a High Power Li-Ion Battery Cathode journal, February 2011

Structural evolution of electrodes in the NCR and CGR cathode-containing commercial lithium-ion batteries cycled between 3.0 and 4.5 V: An operando neutron powder-diffraction study journal, October 2014

Electrochemical kinetics of the 0.5Li2MnO3·0.5LiMn0.42Ni0.42Co0.16O2 ‘composite’ layered cathode material for lithium-ion batteries journal, January 2012

Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment journal, December 2019

Kinetic pathways of ionic transport in fast-charging lithium titanate journal, February 2020

Controlling Covalency and Anion Redox Potentials through Anion Substitution in Li-Rich Chalcogenides journal, December 2020

Injection of oxygen vacancies in the bulk lattice of layered cathodes journal, April 2019

Multielectron, Cation and Anion Redox in Lithium-Rich Iron Sulfide Cathodes journal, March 2020

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

Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration journal, September 2020

Charge Compensation Mechanism of Lithium-Excess Metal Oxides with Different Covalent and Ionic Characters Revealed by Operando Soft and Hard X-ray Absorption Spectroscopy journal, November 2019

High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions journal, February 2019

Exploring the bottlenecks of anionic redox in Li-rich layered sulfides journal, November 2019

Re-entrant Lithium Local Environments and Defect Driven Electrochemistry of Li- and Mn-Rich Li-Ion Battery Cathodes journal, February 2015

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

High resolution x‐ray absorption spectroscopy with absolute energy calibration for the determination of absorption edge energies journal, March 1996

Anionic Redox Activity as a Key Factor in the Performance Degradation of NaFeO 2 Cathodes for Sodium Ion Batteries journal, May 2019

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

Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries journal, November 2016

Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes journal, January 2020

Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries journal, December 2012

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

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005

Challenges for Rechargeable Li Batteries
journal, February 2010

Direct Visualization of the Reversible O ²⁻ /O ⁻ Redox Process in Li-Rich Cathode Materials
journal, February 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

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

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

Understanding the Roles of Anionic Redox and Oxygen Release during Electrochemical Cycling of Lithium-Rich Layered Li ₄ FeSbO ₆
journal, April 2015

Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery
journal, April 2019

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

Oxidation state and chemical shift investigation in transition metal oxides by EELS
journal, May 2012

Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes
journal, January 2020

Two- and three-electrode impedance spectroscopy of lithium-ion batteries
journal, September 2002

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

Origin of voltage decay in high-capacity layered oxide electrodes
journal, December 2014

Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S
journal, October 2019

Direct In situ Observation of Li ₂ O Evolution on Li-Rich High-Capacity Cathode Material, Li[Ni _x Li _{(1–2 x )/3} Mn _{(2– x )/3} ]O ₂ (0 ≤ x ≤0.5)
journal, January 2014

Li 2 FeS 2 , a cathodic material for lithium secondary battery
journal, October 1981

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

Lithium-rich layered titanium sulfides: Cobalt- and Nickel-free high capacity cathode materials for lithium-ion batteries
journal, April 2020

Elucidation of Active Oxygen Sites upon Delithiation of Li ₃ IrO ₄
journal, December 2020

Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries
journal, June 2019

Extended Interfacial Stability through Simple Acid Rinsing in a Li-Rich Oxide Cathode Material
journal, April 2020

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

Atomic-Scale Investigation of Defects, Dopants, and Lithium Transport in the LiFePO ₄ Olivine-Type Battery Material
journal, October 2005

First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk
journal, September 2020

Review of the U.S. Department of Energy’s “Deep Dive” Effort to Understand Voltage Fade in Li- and Mn-Rich Cathodes
journal, October 2015

The Role of Intragranular Nanopores in Capacity Fade of Nickel-Rich Layered Li(Ni _{1– x – y} Co _x Mn _y )O ₂ Cathode Materials
journal, August 2019

Lithium iron thio-phosphate: a new 3 V sulfide cathode
journal, April 2003

Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release
journal, July 2018

Fast Lithium Ion Conduction in Li ₂ SnS ₃ : Synthesis, Physicochemical Characterization, and Electronic Structure
journal, December 2014

Monodisperse Porous LiFePO ₄ Microspheres for a High Power Li-Ion Battery Cathode
journal, February 2011

Structural evolution of electrodes in the NCR and CGR cathode-containing commercial lithium-ion batteries cycled between 3.0 and 4.5 V: An operando neutron powder-diffraction study
journal, October 2014

Electrochemical kinetics of the 0.5Li2MnO3·0.5LiMn0.42Ni0.42Co0.16O2 ‘composite’ layered cathode material for lithium-ion batteries
journal, January 2012

Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment
journal, December 2019

Kinetic pathways of ionic transport in fast-charging lithium titanate
journal, February 2020

Controlling Covalency and Anion Redox Potentials through Anion Substitution in Li-Rich Chalcogenides
journal, December 2020

Injection of oxygen vacancies in the bulk lattice of layered cathodes
journal, April 2019

Multielectron, Cation and Anion Redox in Lithium-Rich Iron Sulfide Cathodes
journal, March 2020

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

Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration
journal, September 2020

Charge Compensation Mechanism of Lithium-Excess Metal Oxides with Different Covalent and Ionic Characters Revealed by Operando Soft and Hard X-ray Absorption Spectroscopy
journal, November 2019

High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions
journal, February 2019

Exploring the bottlenecks of anionic redox in Li-rich layered sulfides
journal, November 2019

Re-entrant Lithium Local Environments and Defect Driven Electrochemistry of Li- and Mn-Rich Li-Ion Battery Cathodes
journal, February 2015

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

High resolution x‐ray absorption spectroscopy with absolute energy calibration for the determination of absorption edge energies
journal, March 1996

Anionic Redox Activity as a Key Factor in the Performance Degradation of NaFeO ₂ Cathodes for Sodium Ion Batteries
journal, May 2019

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

Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries
journal, November 2016

Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes
journal, January 2020

Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries
journal, December 2012