Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials

Qiao, Ruimin; Liu, Jun; Kourtakis, Kostantinos; Roelofs, Mark G.; Peterson, Darin L.; Duff, James P.; Deibler, Dean T.; Wray, L. Andrew; Yang, Wanli

doi:10.1016/j.jpowsour.2017.06.009

Title: Transition-metal redox evolution in LiNi_0.5Mn_0.3Co_0.2O₂ electrodes at high potentials

Abstract

The mixed transition-metal layered compound, LiNi_0.5Mn_0.3Co_0.2O₂ (NMC532), is a promising high-energy cathode material. However, the required high-voltage (>4.3 V) cycling is accompanied by a rapid capacity fade associated with a complex redox mechanism that has not been clarified. Here in this paper, we report soft x-ray absorption spectroscopy of NMC532 electrodes, both pristine and those charged to 4.2, 4.35, or 4.5 V in graphite/NMC532 cells. A quantitative sXAS analysis shows that about 20% of the nickel exists as Ni⁴⁺ in the as-synthesized NMC532. The Ni redox reaction contributes only to the experimental capacity obtained below 4.2 V, while Co redox reactions take place throughout the entire electrochemical cycling up to 4.5 V. In contrast to the changing ratio of the well-defined Ni²⁺, Ni³⁺ and Ni⁴⁺ ions, Co always displays ill-defined intermediate valence states in the charged NMC532 electrodes. This indicates an itinerant electron system in NMC electrodes related to the improved rate performance through Co doping. Furthermore, about 20% of Ni²⁺ is found on the electrode surface at the high potential, which suggests that the electrode surface has either gone through surface reconstruction or reacted with the electrolyte at high voltage.

Authors:

Qiao, Ruimin ^[1]; Liu, Jun ^[2]; Kourtakis, Kostantinos ^[3]; Roelofs, Mark G. ^[3]; Peterson, Darin L. ^[3]; Duff, James P. ^[3]; Deibler, Dean T. ^[3]; Wray, L. Andrew ^[4];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
DuPont Company, Experimental Station, Wilmington, DE (United States)
DuPont Company, Experimental Station, Wilmington, DE (United States)
New York Univ. (NYU), NY (United States). Dept. of Physics

Publication Date:: Mon Jun 12 00:00:00 EDT 2017

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

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

OSTI Identifier:: 1437956

Alternate Identifier(s):: OSTI ID: 1550213

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Power Sources

Additional Journal Information:: Journal Volume: 360; Journal Issue: C; Related Information: © 2017 Elsevier B.V.; Journal ID: ISSN 0378-7753

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; 36 MATERIALS SCIENCE; Lithium-ion batteries; LiNi0.5Mn0.3Co0.2O2; High voltage; Soft x-ray spectroscopy

Citation Formats


                    Qiao, Ruimin, Liu, Jun, Kourtakis, Kostantinos, Roelofs, Mark G., Peterson, Darin L., Duff, James P., Deibler, Dean T., Wray, L. Andrew, and Yang, Wanli. Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials.  United States: N. p., 2017. 
Web.  doi:10.1016/j.jpowsour.2017.06.009.

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                    Qiao, Ruimin, Liu, Jun, Kourtakis, Kostantinos, Roelofs, Mark G., Peterson, Darin L., Duff, James P., Deibler, Dean T., Wray, L. Andrew, & Yang, Wanli. Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials.  United States.  https://doi.org/10.1016/j.jpowsour.2017.06.009

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                    Qiao, Ruimin, Liu, Jun, Kourtakis, Kostantinos, Roelofs, Mark G., Peterson, Darin L., Duff, James P., Deibler, Dean T., Wray, L. Andrew, and Yang, Wanli. Mon .  
"Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials".  United States.  https://doi.org/10.1016/j.jpowsour.2017.06.009.  https://www.osti.gov/servlets/purl/1437956.

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@article{osti_1437956,

  title        = {Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials},

  author       = {Qiao, Ruimin and Liu, Jun and Kourtakis, Kostantinos and Roelofs, Mark G. and Peterson, Darin L. and Duff, James P. and Deibler, Dean T. and Wray, L. Andrew and Yang, Wanli},

  abstractNote = {The mixed transition-metal layered compound, LiNi0.5Mn0.3Co0.2O2 (NMC532), is a promising high-energy cathode material. However, the required high-voltage (>4.3 V) cycling is accompanied by a rapid capacity fade associated with a complex redox mechanism that has not been clarified. Here in this paper, we report soft x-ray absorption spectroscopy of NMC532 electrodes, both pristine and those charged to 4.2, 4.35, or 4.5 V in graphite/NMC532 cells. A quantitative sXAS analysis shows that about 20% of the nickel exists as Ni4+ in the as-synthesized NMC532. The Ni redox reaction contributes only to the experimental capacity obtained below 4.2 V, while Co redox reactions take place throughout the entire electrochemical cycling up to 4.5 V. In contrast to the changing ratio of the well-defined Ni2+, Ni3+ and Ni4+ ions, Co always displays ill-defined intermediate valence states in the charged NMC532 electrodes. This indicates an itinerant electron system in NMC electrodes related to the improved rate performance through Co doping. Furthermore, about 20% of Ni2+ is found on the electrode surface at the high potential, which suggests that the electrode surface has either gone through surface reconstruction or reacted with the electrolyte at high voltage.},

  doi          = {10.1016/j.jpowsour.2017.06.009},

  journal      = {Journal of Power Sources},

  number       = C,

  volume       = 360,

  place        = {United States},

  year         = {Mon Jun 12 00:00:00 EDT 2017},

  month        = {Mon Jun 12 00:00:00 EDT 2017}

}

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Title: Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials

Abstract

Citation Formats

Issues and challenges facing rechargeable lithium batteries journal, November 2001

The Li-Ion Rechargeable Battery: A Perspective journal, January 2013

Positive Electrode Materials for Li-Ion and Li-Batteries † journal, February 2010

Challenges for Rechargeable Li Batteries journal, February 2010

Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li 1 - x Co 1/3 Ni 1/3 Mn 1/3 O 2 Electrode System by Combination of Soft and Hard X-ray Absorption Spectroscopy journal, December 2005

Interfacial Origin of Performance Improvement and Fade for 4.6 V LiNi 0.5 Co 0.2 Mn 0.3 O 2 Battery Cathodes journal, May 2014

Combining In Situ Synchrotron X-Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium-Ion Batteries journal, June 2012

Structural characterization of layered LiNi0.85−xMnxCo0.15O2 with x=0, 0.1, 0.2 and 0.4 oxide electrodes for Li batteries journal, July 2011

Enhancing the High-Voltage Cycling Performance of LiNi 0.5 Mn 0.3 Co 0.2 O 2 by Retarding Its Interfacial Reaction with an Electrolyte by Atomic-Layer-Deposited Al 2 O 3 journal, November 2015

Structural Changes and Thermal Stability of Charged LiNi x Mn y Co z O 2 Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy journal, December 2014

Investigating the Reversibility of Structural Modifications of Li x Ni y Mn z Co 1– y – z O 2 Cathode Materials during Initial Charge/Discharge, at Multiple Length Scales journal, August 2015

Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes journal, June 2015

Local electronic and geometrical structure of LaNi 1 − x Mn x O 3 + δ perovskites determined by x-ray-absorption spectroscopy journal, March 2002

Electrochemical Activities in Li[sub 2]MnO[sub 3] journal, January 2009

Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li 2 MnO 3 −LiCo 1/3 Ni 1/3 Mn 1/3 O 2 journal, March 2011

Mn K -edge XANES study of the La 1 − x Ca x MnO 3 colossal magnetoresistive manganites journal, June 2001

The first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V journal, March 2004

Ligand field strengths and oxidation states from manganese L-edge spectroscopy journal, October 1991

Multiple Scattering Calculations of Bonding and X-ray Absorption Spectroscopy of Manganese Oxides journal, April 2003

Changes in electronic structure of the electrochemically Li-ion deintercalated LiMn2O4 system investigated by soft X-ray absorption spectroscopy journal, June 2003

Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy journal, September 2016

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5 Mn 1.5 O 4 Electrodes journal, November 2015

Direct evidence of gradient Mn(II) evolution at charged states in LiNi0.5Mn1.5O4 electrodes with capacity fading journal, January 2015

Revealing and suppressing surface Mn(II) formation of Na0.44MnO2 electrodes for Na-ion batteries journal, September 2015

Key electronic states in lithium battery materials probed by soft X-ray spectroscopy journal, October 2013

Distinct Solid-Electrolyte-Interphases on Sn (100) and (001) Electrodes Studied by Soft X-Ray Spectroscopy journal, February 2014

Charge Transfer Excitation in Resonant X-ray Emission Spectroscopy of NiO journal, July 2005

Spin-orbit-induced mixed-spin ground state in R Ni O 3 perovskites probed by x-ray absorption spectroscopy: Insight into the metal-to-insulator transition journal, January 2005

Improving the electrochemical properties of LiNi 0.5 Co 0.2 Mn 0.3 O 2 at 4.6 V cutoff potential by surface coating with Li 2 TiO 3 for lithium-ion batteries journal, January 2015

Strong interference between decay channels and valence-electron rearrangements in core-hole spectroscopy journal, June 1986

2 p x-ray absorption of 3 d transition-metal compounds: An atomic multiplet description including the crystal field journal, September 1990

Phase Transformation and Lithiation Effect on Electronic Structure of Li x FePO 4 : An In-Depth Study by Soft X-ray and Simulations journal, August 2012

In Situ Formation of a Cathode-Electrolyte Interface with Enhanced Stability by Titanium Substitution for High Voltage Spinel Lithium-Ion Batteries journal, May 2015

Role of Oxygen Holes in Li x CoO 2 Revealed by Soft X-Ray Spectroscopy journal, August 2013

Understanding the capacity fading mechanism in LiNi0.5Mn1.5O4/graphite Li-ion batteries journal, February 2013

Dissolution of Spinel Oxides and Capacity Losses in 4V Li / LixMn2O4 Cells journal, January 1996

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal, March 2014

Insight into the Atomic Structure of High-Voltage Spinel LiNi 0.5 Mn 1.5 O 4 Cathode Material in the First Cycle journal, December 2014

Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy journal, October 2013

Oxygen 1 s x-ray-absorption edges of transition-metal oxides journal, September 1989

The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials journal, May 2016

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

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

Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2 journal, February 2015

Reversible Anionic Redox Activities in Conventional LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathodes journal, March 2020

Improving the Cycling Performance of High-Voltage NMC111 || Graphite Lithium Ion Cells By an Effective Urea-Based Electrolyte Additive journal, January 2019

First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material x Li 2 MnO 3 ⋅ (1- x )Li M O 2 ( x = 0.4) journal, January 2018

Revisiting the charge compensation mechanisms in LiNi 0.8 Co 0.2−y Al y O 2 systems journal, January 2019

Reversible Anionic Redox Activities in Conventional LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathodes journal, March 2020

Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes. journalarticle, January 2019

Title: Transition-metal redox evolution in LiNi_0.5Mn_0.3Co_0.2O₂ electrodes at high potentials

Issues and challenges facing rechargeable lithium batteries
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The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

Positive Electrode Materials for Li-Ion and Li-Batteries ^†
journal, February 2010

Challenges for Rechargeable Li Batteries
journal, February 2010

Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li ₁ _- _x Co _1/3 Ni _1/3 Mn _1/3 O ₂ Electrode System by Combination of Soft and Hard X-ray Absorption Spectroscopy
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Interfacial Origin of Performance Improvement and Fade for 4.6 V LiNi _0.5 Co _0.2 Mn _0.3 O ₂ Battery Cathodes
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Combining In Situ Synchrotron X-Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium-Ion Batteries
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Structural characterization of layered LiNi0.85−xMnxCo0.15O2 with x=0, 0.1, 0.2 and 0.4 oxide electrodes for Li batteries
journal, July 2011

Enhancing the High-Voltage Cycling Performance of LiNi _0.5 Mn _0.3 Co _0.2 O ₂ by Retarding Its Interfacial Reaction with an Electrolyte by Atomic-Layer-Deposited Al ₂ O ₃
journal, November 2015

Structural Changes and Thermal Stability of Charged LiNi _x Mn _y Co _z O ₂ Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy
journal, December 2014

Investigating the Reversibility of Structural Modifications of Li _x Ni _y Mn _z Co _{1– y – z} O ₂ Cathode Materials during Initial Charge/Discharge, at Multiple Length Scales
journal, August 2015

Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes
journal, June 2015

Local electronic and geometrical structure of ${LaNi}_{1 - x} {Mn}_{x} O_{3 + δ}$ perovskites determined by x-ray-absorption spectroscopy
journal, March 2002

Electrochemical Activities in Li[sub 2]MnO[sub 3]
journal, January 2009

Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li ₂ MnO ₃ −LiCo _1/3 Ni _1/3 Mn _1/3 O ₂
journal, March 2011

$Mn$ K -edge XANES study of the ${La}_{1 - x} {Ca}_{x} {MnO}_{3}$ colossal magnetoresistive manganites
journal, June 2001

The first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V
journal, March 2004

Ligand field strengths and oxidation states from manganese L-edge spectroscopy
journal, October 1991

Multiple Scattering Calculations of Bonding and X-ray Absorption Spectroscopy of Manganese Oxides
journal, April 2003

Changes in electronic structure of the electrochemically Li-ion deintercalated LiMn2O4 system investigated by soft X-ray absorption spectroscopy
journal, June 2003

Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy
journal, September 2016

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi _0.5 Mn _1.5 O ₄ Electrodes
journal, November 2015

Direct evidence of gradient Mn(II) evolution at charged states in LiNi0.5Mn1.5O4 electrodes with capacity fading
journal, January 2015

Revealing and suppressing surface Mn(II) formation of Na0.44MnO2 electrodes for Na-ion batteries
journal, September 2015

Key electronic states in lithium battery materials probed by soft X-ray spectroscopy
journal, October 2013

Distinct Solid-Electrolyte-Interphases on Sn (100) and (001) Electrodes Studied by Soft X-Ray Spectroscopy
journal, February 2014

Charge Transfer Excitation in Resonant X-ray Emission Spectroscopy of NiO
journal, July 2005

Spin-orbit-induced mixed-spin ground state in $R Ni O_{3}$ perovskites probed by x-ray absorption spectroscopy: Insight into the metal-to-insulator transition
journal, January 2005

Improving the electrochemical properties of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ at 4.6 V cutoff potential by surface coating with Li ₂ TiO ₃ for lithium-ion batteries
journal, January 2015

Strong interference between decay channels and valence-electron rearrangements in core-hole spectroscopy
journal, June 1986

2 p x-ray absorption of 3 d transition-metal compounds: An atomic multiplet description including the crystal field
journal, September 1990

Phase Transformation and Lithiation Effect on Electronic Structure of Li _x FePO ₄ : An In-Depth Study by Soft X-ray and Simulations
journal, August 2012

In Situ Formation of a Cathode-Electrolyte Interface with Enhanced Stability by Titanium Substitution for High Voltage Spinel Lithium-Ion Batteries
journal, May 2015

Role of Oxygen Holes in ${Li}_{x} {CoO}_{2}$ Revealed by Soft X-Ray Spectroscopy
journal, August 2013

Understanding the capacity fading mechanism in LiNi0.5Mn1.5O4/graphite Li-ion batteries
journal, February 2013

Dissolution of Spinel Oxides and Capacity Losses in 4V Li / Li_xMn₂O₄ Cells
journal, January 1996

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014

Insight into the Atomic Structure of High-Voltage Spinel LiNi _0.5 Mn _1.5 O ₄ Cathode Material in the First Cycle
journal, December 2014

Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy
journal, October 2013

Oxygen 1 s x-ray-absorption edges of transition-metal oxides
journal, September 1989

The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials
journal, May 2016

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

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

Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2
journal, February 2015

Reversible Anionic Redox Activities in Conventional LiNi _1/3 Co _1/3 Mn _1/3 O ₂ Cathodes
journal, March 2020

Improving the Cycling Performance of High-Voltage NMC111 || Graphite Lithium Ion Cells By an Effective Urea-Based Electrolyte Additive
journal, January 2019

First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material x Li ₂ MnO ₃ ⋅ (1- x )Li M O ₂ ( x = 0.4)
journal, January 2018

Revisiting the charge compensation mechanisms in LiNi _0.8 Co _0.2−y Al _y O ₂ systems
journal, January 2019

Reversible Anionic Redox Activities in Conventional LiNi _1/3 Co _1/3 Mn _1/3 O ₂ Cathodes
journal, March 2020

Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes.
journalarticle, January 2019