Synthesis, Structure, and Electrochemical Performance of High Capacity Li2Cu0.5Ni0.5O2 Cathodes

Ruther, Rose E; Zhou, Hui; Dhital, Chetan; Saravanan, Kuppan; Kercher, Andrew K.; Chen, Guoying; Huq, Ashfia; Delnick, Frank M.; Nanda, Jagjit

doi:10.1021/acs.chemmater.5b02843

Title: Synthesis, Structure, and Electrochemical Performance of High Capacity Li₂Cu_0.5Ni_0.5O₂ Cathodes

Abstract

Orthorhombic Li₂NiO₂, Li₂CuO₂, and solid solutions thereof have been studied as potential cathode materials for lithium-ion batteries due to their high theoretical capacity and relatively low cost. While neither endmember shows good cycling stability, the intermediate composition, Li₂Cu_0.5Ni_0.5O₂, yields reasonably high reversible capacities. A new synthetic approach and detailed characterization of this phase and the parent Li₂CuO₂ are presented. The cycle life of Li₂Cu_0.5Ni_0.5O₂ is shown to depend critically on the voltage window. The formation of Cu¹⁺ at low voltage and oxygen evolution at high voltage limit the electrochemical reversibility. In situ X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and gas evolution measurements are used to follow the chemical and structural changes that occur as a function of cell voltage.

Authors:

Ruther, Rose E ^[1]; Zhou, Hui ^[1]; Dhital, Chetan ^[1]; Saravanan, Kuppan ^[2]; Kercher, Andrew K. ^[1]; Chen, Guoying ^[2]; Huq, Ashfia ^[1]; Delnick, Frank M. ^[1]; Nanda, Jagjit ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Tue Sep 08 00:00:00 EDT 2015

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:: 1215600

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Chemistry of Materials

Additional Journal Information:: Journal Volume: 27; Journal Issue: 19; Journal ID: ISSN 0897-4756

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 25 ENERGY STORAGE

Citation Formats


                    Ruther, Rose E, Zhou, Hui, Dhital, Chetan, Saravanan, Kuppan, Kercher, Andrew K., Chen, Guoying, Huq, Ashfia, Delnick, Frank M., and Nanda, Jagjit. Synthesis, Structure, and Electrochemical Performance of High Capacity Li2Cu0.5Ni0.5O2 Cathodes.  United States: N. p., 2015. 
Web.  doi:10.1021/acs.chemmater.5b02843.

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                    Ruther, Rose E, Zhou, Hui, Dhital, Chetan, Saravanan, Kuppan, Kercher, Andrew K., Chen, Guoying, Huq, Ashfia, Delnick, Frank M., & Nanda, Jagjit. Synthesis, Structure, and Electrochemical Performance of High Capacity Li2Cu0.5Ni0.5O2 Cathodes.  United States.  https://doi.org/10.1021/acs.chemmater.5b02843

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                    Ruther, Rose E, Zhou, Hui, Dhital, Chetan, Saravanan, Kuppan, Kercher, Andrew K., Chen, Guoying, Huq, Ashfia, Delnick, Frank M., and Nanda, Jagjit. Tue .  
"Synthesis, Structure, and Electrochemical Performance of High Capacity Li2Cu0.5Ni0.5O2 Cathodes".  United States.  https://doi.org/10.1021/acs.chemmater.5b02843.  https://www.osti.gov/servlets/purl/1215600.

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@article{osti_1215600,

  title        = {Synthesis, Structure, and Electrochemical Performance of High Capacity Li2Cu0.5Ni0.5O2 Cathodes},

  author       = {Ruther, Rose E and Zhou, Hui and Dhital, Chetan and Saravanan, Kuppan and Kercher, Andrew K. and Chen, Guoying and Huq, Ashfia and Delnick, Frank M. and Nanda, Jagjit},

  abstractNote = {Orthorhombic Li2NiO2, Li2CuO2, and solid solutions thereof have been studied as potential cathode materials for lithium-ion batteries due to their high theoretical capacity and relatively low cost. While neither endmember shows good cycling stability, the intermediate composition, Li2Cu0.5Ni0.5O2, yields reasonably high reversible capacities. A new synthetic approach and detailed characterization of this phase and the parent Li2CuO2 are presented. The cycle life of Li2Cu0.5Ni0.5O2 is shown to depend critically on the voltage window. The formation of Cu1+ at low voltage and oxygen evolution at high voltage limit the electrochemical reversibility. In situ X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and gas evolution measurements are used to follow the chemical and structural changes that occur as a function of cell voltage.},

  doi          = {10.1021/acs.chemmater.5b02843},

  journal      = {Chemistry of Materials},

  number       = 19,

  volume       = 27,

  place        = {United States},

  year         = {Tue Sep 08 00:00:00 EDT 2015},

  month        = {Tue Sep 08 00:00:00 EDT 2015}

}

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https://doi.org/10.1021/acs.chemmater.5b02843

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Title: Synthesis, Structure, and Electrochemical Performance of High Capacity Li2Cu0.5Ni0.5O2 Cathodes

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Citation Formats

Particle Size Effects on the Electrochemical Performance of Copper Oxides toward Lithium journal, January 2001

Preparation and Electrochemical Performance of Polycrystalline and Single Crystalline CuO Nanorods as Anode Materials for Li Ion Battery journal, May 2004

Reactivity of transition metal (Co, Ni, Cu) sulphides versus lithium: The intriguing case of the copper sulphide journal, June 2006

Gram-Scale Synthesis of Cu 2 O Nanocubes and Subsequent Oxidation to CuO Hollow Nanostructures for Lithium-Ion Battery Anode Materials journal, February 2009

Investigation of the Conversion Reaction Mechanisms for Binary Copper(II) Compounds by Solid-State NMR Spectroscopy and X-ray Diffraction journal, July 2009

Self-assembled synthesis of hierarchical nanostructured CuO with various morphologies and their application as anodes for lithium ion batteries journal, January 2010

Lithium Copper Oxide Lithium Copper Oxyphosphate Battery Systems journal, August 1986

High temperature electrochemical discharges of lithium-copper oxide cells using solid electrolytes journal, May 1994

A high-temperature lithiumcopper oxide cell with a solid polymer electrolyte journal, October 1991

CuO cathode in lithium cells—II. Reduction mechanism of CuO journal, December 1985

CuO cathode in lithium cells journal, June 1985

The influence of preparation conditions on the electrochemical behaviour of CuO in a Li/CuO cell journal, April 1985

Beyond Divalent Copper: A Redox Couple for Sodium Ion Battery Cathode Materials journal, January 2015

Novel copper redox-based cathode materials for room-temperature sodium-ion batteries journal, November 2014

LiNi x Cu0.5 − x Mn1.5 O 4 Spinel Electrodes, Superior High‐Potential Cathode Materials for Li Batteries: I. Electrochemical and Structural Studies journal, March 1999

LiCu x Mn2 − x O 4 Spinels ( 0.1 ⩽ x ⩽ 0.5 ) : A New Class of Cathode Materials for Li Batteries: II. In Situ Measurements journal, October 1998

LiMn2 − x Cu x O 4 Spinels (0.1 ⩽ x ⩽ 0.5): A new Class of 5 V Cathode Materials for Li Batteries: I. Electrochemical, Structural, and Spectroscopic Studies journal, April 1998

LiCu x II Cu y III Mn [ 2 − ( x + y ) ] III , IV O 4 : 5 V Cathode Materials journal, August 1997

Li 2 Cu 2 O(SO 4 ) 2 : a Possible Electrode for Sustainable Li-Based Batteries Showing a 4.7 V Redox Activity vs Li + /Li 0 journal, April 2015

Electrochemical and structural study of Li2CuO2, LiCuO2 and NaCuO2 journal, February 1998

Synthesis, Phase Stability, and Electrochemically Driven Transformations in the LiCuO 2 −Li 2 CuO 2 System journal, August 2005

Preparation and electrochemical properties of a Li2CuO2–Li2NiO2 solid solution as a lithium-intercalation electrode journal, June 2006

Characterization and Electrochemical Properties of Li2Cu0.5Ni0.4M0.1O2 Lithium-ion Battery Cathodes journal, August 2009

Structural originations of irreversible capacity loss from highly lithiated copper oxides journal, September 2011

Structural changes and electrochemical properties of Li2Cu1−M O2 for lithium secondary batteries journal, September 2014

Electrochemical Properties and Gas Evolution Behavior of Overlithiated Li 2 NiO 2 as Cathode Active Mass for Rechargeable Li Ion Batteries journal, January 2012

Synthesis, Electrochemical Properties, and Phase Stability of Li 2 NiO 2 with the Immm Structure journal, June 2004

Structure and electrochemistry of Li1±yNiO2 and a new Li2NiO2 phase with the Ni (OH)2 structure journal, December 1990

Structure of 1T-Li2NiO2 from powder neutron diffraction journal, July 1991

Origin of the band gap in the negative charge-transfer-energy compound NaCuO 2 journal, September 1991

Nature of hole states in cuprate superconductors journal, November 1992

Room temperature synthesis and structural characterization of monoclinic LiCuO2 by X-ray and neutron diffraction journal, January 1994

The structure of Li3Cu2O4, a compound with formal mixed valence journal, January 1993

Li2CuO2 as an additive for capacity enhancement of lithium ion cells journal, June 2003

Lithium transport in ternary lithium-copper-oxygen cathode materials journal, January 1986

The thermochemistry of LiCuO, Li2CuO2 and LiCu2O2 journal, July 1991

Thermodynamic investigations of copper oxides used as conversion type electrodes in lithium ion batteries journal, April 2013

A Survey of first-row ternary oxides LiMO2 (M = Sc-Cu) journal, January 1987

Synthesis and structure of lithium cuprate Li3Cu2O4 journal, January 1991

Preparation, Crystal Structure and Magnetic Property of a New Compound LiCuO 2 journal, May 1992

Structure of the mixed-valence lithium cuprate Li3Cu2O4 by powder neutron diffraction journal, January 1993

XAS Investigation of Inhomogeneous Metal-Oxygen Bond Covalency in Bulk and Surface for Charge Compensation in Li-Ion Battery Cathode Li[Ni[sub 1∕3]Co[sub 1∕3]Mn[sub 1∕3]]O[sub 2] Material journal, January 2005

Electronic structure variation of the surface and bulk of a LiNi 0.5 Mn 1.5 O 4 cathode as a function of state of charge: X-ray absorption spectroscopic study journal, January 2014

Crystal Structures and Electrochemical Properties of Ni-Substituted Li2CuO2 as a Cathode Material journal, April 2013

Hydrogen evolution at the negative electrode of the all-vanadium redox flow batteries journal, February 2014

EXPGUI , a graphical user interface for GSAS journal, April 2001

Lithium Cuprate (Li 2 CuO 2 ): A New Possible Ceramic Material for CO 2 Chemisorption journal, August 2008

Structural Analysis and CO 2 Chemisorption Study on Nonstoichiometric Lithium Cuprates (Li 2+ x CuO 2+ x /2 ) journal, December 2008

Vibrational Properties of CuO and Cu 4 O 3 from First-Principles Calculations, and Raman and Infrared Spectroscopy journal, May 2012

Comparative study of LiCoO2, LiNi12Co12O2 and LiNiO2 for 4 volt secondary lithium cells journal, June 1993

Various strategies to tune the ionic/electronic properties of electrode materials journal, January 2004

Various aspects of LiNiO 2 chemistry: A review journal, January 2005

Raman Microspectrometry Applied to the Study of Electrode Materials for Lithium Batteries journal, March 2010

Design of electrolyte solutions for Li and Li-ion batteries: a review journal, November 2004

Sputter-Deposited Amorphous LiCuPO 4 Thin Film as Cathode Material for Li-ion Microbatteries journal, January 2018

In situ analytical techniques for battery interface analysis journal, January 2018

Studies on the local structures for the trigonal Ni 3+ centers in cathode materials LiAl y Co 1-y O 2 ( y = 0, 0.1, 0.5, and 0.8) journal, May 2018

Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries journal, January 2019

Long-Term Chemothermal Stability of Delithiated NCA in Polymer Solid-State Batteries text, January 2019

Investigation of the Phase Transition Mechanism in LiFePO4 Cathode Using In Situ Raman Spectroscopy and 2D Correlation Spectroscopy during Initial Cycle journal, January 2019

Title: Synthesis, Structure, and Electrochemical Performance of High Capacity Li₂Cu_0.5Ni_0.5O₂ Cathodes

Particle Size Effects on the Electrochemical Performance of Copper Oxides toward Lithium
journal, January 2001

Preparation and Electrochemical Performance of Polycrystalline and Single Crystalline CuO Nanorods as Anode Materials for Li Ion Battery
journal, May 2004

Reactivity of transition metal (Co, Ni, Cu) sulphides versus lithium: The intriguing case of the copper sulphide
journal, June 2006

Gram-Scale Synthesis of Cu ₂ O Nanocubes and Subsequent Oxidation to CuO Hollow Nanostructures for Lithium-Ion Battery Anode Materials
journal, February 2009

Investigation of the Conversion Reaction Mechanisms for Binary Copper(II) Compounds by Solid-State NMR Spectroscopy and X-ray Diffraction
journal, July 2009

Self-assembled synthesis of hierarchical nanostructured CuO with various morphologies and their application as anodes for lithium ion batteries
journal, January 2010

Lithium Copper Oxide Lithium Copper Oxyphosphate Battery Systems
journal, August 1986

High temperature electrochemical discharges of lithium-copper oxide cells using solid electrolytes
journal, May 1994

A high-temperature lithiumcopper oxide cell with a solid polymer electrolyte
journal, October 1991

CuO cathode in lithium cells—II. Reduction mechanism of CuO
journal, December 1985

CuO cathode in lithium cells
journal, June 1985

The influence of preparation conditions on the electrochemical behaviour of CuO in a Li/CuO cell
journal, April 1985

Beyond Divalent Copper: A Redox Couple for Sodium Ion Battery Cathode Materials
journal, January 2015

Novel copper redox-based cathode materials for room-temperature sodium-ion batteries
journal, November 2014

LiNi x Cu0.5 − x Mn1.5 O 4 Spinel Electrodes, Superior High‐Potential Cathode Materials for Li Batteries: I. Electrochemical and Structural Studies
journal, March 1999

LiCu x Mn2 − x O 4 Spinels ( 0.1 ⩽ x ⩽ 0.5 ) : A New Class of Cathode Materials for Li Batteries: II. In Situ Measurements
journal, October 1998

LiMn2 − x Cu x O 4 Spinels (0.1 ⩽ x ⩽ 0.5): A new Class of 5 V Cathode Materials for Li Batteries: I. Electrochemical, Structural, and Spectroscopic Studies
journal, April 1998

LiCu x II Cu y III Mn [ 2 − ( x + y ) ] III , IV O 4 : 5 V Cathode Materials
journal, August 1997

Li ₂ Cu ₂ O(SO ₄ ) ₂ : a Possible Electrode for Sustainable Li-Based Batteries Showing a 4.7 V Redox Activity vs Li ⁺ /Li ⁰
journal, April 2015

Electrochemical and structural study of Li2CuO2, LiCuO2 and NaCuO2
journal, February 1998

Synthesis, Phase Stability, and Electrochemically Driven Transformations in the LiCuO ₂ −Li ₂ CuO ₂ System
journal, August 2005

Preparation and electrochemical properties of a Li2CuO2–Li2NiO2 solid solution as a lithium-intercalation electrode
journal, June 2006

Characterization and Electrochemical Properties of Li2Cu0.5Ni0.4M0.1O2 Lithium-ion Battery Cathodes
journal, August 2009

Structural originations of irreversible capacity loss from highly lithiated copper oxides
journal, September 2011

Structural changes and electrochemical properties of Li2Cu1−M O2 for lithium secondary batteries
journal, September 2014

Electrochemical Properties and Gas Evolution Behavior of Overlithiated Li ₂ NiO ₂ as Cathode Active Mass for Rechargeable Li Ion Batteries
journal, January 2012

Synthesis, Electrochemical Properties, and Phase Stability of Li ₂ NiO ₂ with the Immm Structure
journal, June 2004

Structure and electrochemistry of Li1±yNiO2 and a new Li2NiO2 phase with the Ni (OH)2 structure
journal, December 1990

Structure of 1T-Li2NiO2 from powder neutron diffraction
journal, July 1991

Origin of the band gap in the negative charge-transfer-energy compound ${NaCuO}_{2}$
journal, September 1991

Nature of hole states in cuprate superconductors
journal, November 1992

Room temperature synthesis and structural characterization of monoclinic LiCuO2 by X-ray and neutron diffraction
journal, January 1994

The structure of Li3Cu2O4, a compound with formal mixed valence
journal, January 1993

Li2CuO2 as an additive for capacity enhancement of lithium ion cells
journal, June 2003

Lithium transport in ternary lithium-copper-oxygen cathode materials
journal, January 1986

The thermochemistry of LiCuO, Li2CuO2 and LiCu2O2
journal, July 1991

Thermodynamic investigations of copper oxides used as conversion type electrodes in lithium ion batteries
journal, April 2013

A Survey of first-row ternary oxides LiMO2 (M = Sc-Cu)
journal, January 1987

Synthesis and structure of lithium cuprate Li3Cu2O4
journal, January 1991

Preparation, Crystal Structure and Magnetic Property of a New Compound LiCuO ₂
journal, May 1992

Structure of the mixed-valence lithium cuprate Li3Cu2O4 by powder neutron diffraction
journal, January 1993

XAS Investigation of Inhomogeneous Metal-Oxygen Bond Covalency in Bulk and Surface for Charge Compensation in Li-Ion Battery Cathode Li[Ni[sub 1∕3]Co[sub 1∕3]Mn[sub 1∕3]]O[sub 2] Material
journal, January 2005

Electronic structure variation of the surface and bulk of a LiNi _0.5 Mn _1.5 O ₄ cathode as a function of state of charge: X-ray absorption spectroscopic study
journal, January 2014

Crystal Structures and Electrochemical Properties of Ni-Substituted Li2CuO2 as a Cathode Material
journal, April 2013

Hydrogen evolution at the negative electrode of the all-vanadium redox flow batteries
journal, February 2014

EXPGUI , a graphical user interface for GSAS
journal, April 2001

Lithium Cuprate (Li ₂ CuO ₂ ): A New Possible Ceramic Material for CO ₂ Chemisorption
journal, August 2008

Structural Analysis and CO ₂ Chemisorption Study on Nonstoichiometric Lithium Cuprates (Li _{2+ x} CuO _{2+ x /2} )
journal, December 2008

Vibrational Properties of CuO and Cu ₄ O ₃ from First-Principles Calculations, and Raman and Infrared Spectroscopy
journal, May 2012

Comparative study of LiCoO2, LiNi12Co12O2 and LiNiO2 for 4 volt secondary lithium cells
journal, June 1993

Various strategies to tune the ionic/electronic properties of electrode materials
journal, January 2004

Various aspects of LiNiO ₂ chemistry: A review
journal, January 2005

Raman Microspectrometry Applied to the Study of Electrode Materials for Lithium Batteries
journal, March 2010

Design of electrolyte solutions for Li and Li-ion batteries: a review
journal, November 2004

Sputter-Deposited Amorphous LiCuPO ₄ Thin Film as Cathode Material for Li-ion Microbatteries
journal, January 2018

In situ analytical techniques for battery interface analysis
journal, January 2018

Studies on the local structures for the trigonal Ni ³⁺ centers in cathode materials LiAl _y Co _1-y O ₂ ( y = 0, 0.1, 0.5, and 0.8)
journal, May 2018

Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries
journal, January 2019

Long-Term Chemothermal Stability of Delithiated NCA in Polymer Solid-State Batteries
text, January 2019

Investigation of the Phase Transition Mechanism in LiFePO4 Cathode Using In Situ Raman Spectroscopy and 2D Correlation Spectroscopy during Initial Cycle
journal, January 2019