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Title: Anion-redox nanolithia cathodes for Li-ion batteries

Abstract

The development of lithium-air batteries is plagued by a high potential gap (>1.2 V) between charge and discharge, and poor cyclability due to the drastic phase change of O-2 (gas) and Ox- (condensed phase) at the cathode during battery operations. Here we report a cathode consisting of nanoscale amorphous lithia (nanolithia) confined in a cobalt oxide, enabling charge/discharge between solid Li2O/Li2O2/LiO2 without any gas evolution. The cathode has a theoretical capacity of 1,341 Ah kg(-1), a mass density exceeding 2.2 g cm(-3), and a practical discharge capacity of 587 Ah kg(-1) at 2.55V versus Li/Li+. It also displays stable cycling performance (only 1.8% loss after 130 cycles in lithium-matched full-cell tests against Li4Ti5O12 anode), as well as a round-trip overpotential of only 0.24V. Interestingly, the cathode is automatically protected from O-2 gas release and overcharging through the shuttling of self-generated radical species soluble in the carbonate electrolyte.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technologies (VTO); National Science Foundation (NSF)
OSTI Identifier:
1529959
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 1
Country of Publication:
United States
Language:
English

Citation Formats

Zhu, Zhi, Kushima, Akihiro, Yin, Zongyou, Qi, Lu, Amine, Khalil, Lu, Jun, and Li, Ju. Anion-redox nanolithia cathodes for Li-ion batteries. United States: N. p., 2016. Web. doi:10.1038/NENERGY.2016.111.
Zhu, Zhi, Kushima, Akihiro, Yin, Zongyou, Qi, Lu, Amine, Khalil, Lu, Jun, & Li, Ju. Anion-redox nanolithia cathodes for Li-ion batteries. United States. doi:10.1038/NENERGY.2016.111.
Zhu, Zhi, Kushima, Akihiro, Yin, Zongyou, Qi, Lu, Amine, Khalil, Lu, Jun, and Li, Ju. Mon . "Anion-redox nanolithia cathodes for Li-ion batteries". United States. doi:10.1038/NENERGY.2016.111.
@article{osti_1529959,
title = {Anion-redox nanolithia cathodes for Li-ion batteries},
author = {Zhu, Zhi and Kushima, Akihiro and Yin, Zongyou and Qi, Lu and Amine, Khalil and Lu, Jun and Li, Ju},
abstractNote = {The development of lithium-air batteries is plagued by a high potential gap (>1.2 V) between charge and discharge, and poor cyclability due to the drastic phase change of O-2 (gas) and Ox- (condensed phase) at the cathode during battery operations. Here we report a cathode consisting of nanoscale amorphous lithia (nanolithia) confined in a cobalt oxide, enabling charge/discharge between solid Li2O/Li2O2/LiO2 without any gas evolution. The cathode has a theoretical capacity of 1,341 Ah kg(-1), a mass density exceeding 2.2 g cm(-3), and a practical discharge capacity of 587 Ah kg(-1) at 2.55V versus Li/Li+. It also displays stable cycling performance (only 1.8% loss after 130 cycles in lithium-matched full-cell tests against Li4Ti5O12 anode), as well as a round-trip overpotential of only 0.24V. Interestingly, the cathode is automatically protected from O-2 gas release and overcharging through the shuttling of self-generated radical species soluble in the carbonate electrolyte.},
doi = {10.1038/NENERGY.2016.111},
journal = {Nature Energy},
number = ,
volume = 1,
place = {United States},
year = {2016},
month = {7}
}

Works referenced in this record:

Precise preparation of high performance spherical hierarchical LiNi0.5Mn1.5O4 for 5 V lithium ion secondary batteries
journal, January 2013

  • Zhu, Zhi; Zhang, Ding; Yan, Hui
  • Journal of Materials Chemistry A, Vol. 1, Issue 18
  • DOI: 10.1039/c3ta10980a

A lithium–oxygen battery based on lithium superoxide
journal, January 2016

  • Lu, Jun; Jung Lee, Yun; Luo, Xiangyi
  • Nature, Vol. 529, Issue 7586, p. 377-382
  • DOI: 10.1038/nature16484

Aprotic and Aqueous Li–O2 Batteries
journal, April 2014

  • Lu, Jun; Li, Li; Park, Jin-Bum
  • Chemical Reviews, Vol. 114, Issue 11, p. 5611-5640
  • DOI: 10.1021/cr400573b

α-MnO2 Nanowires: A Catalyst for the O2 Electrode in Rechargeable Lithium Batteries
journal, June 2008

  • Débart, Aurélie; Paterson, Allan J.; Bao, Jianli
  • Angewandte Chemie, Vol. 120, Issue 24
  • DOI: 10.1002/ange.200705648

Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge
journal, January 2013

  • Adams, Brian D.; Radtke, Claudio; Black, Robert
  • Energy & Environmental Science, Vol. 6, Issue 6
  • DOI: 10.1039/c3ee40697k

Charging/Discharging Nanomorphology Asymmetry and Rate-Dependent Capacity Degradation in Li–Oxygen Battery
journal, November 2015


Platinum−Gold Nanoparticles: A Highly Active Bifunctional Electrocatalyst for Rechargeable Lithium−Air Batteries
journal, September 2010

  • Lu, Yi-Chun; Xu, Zhichuan; Gasteiger, Hubert A.
  • Journal of the American Chemical Society, Vol. 132, Issue 35, p. 12170-12171
  • DOI: 10.1021/ja1036572

Interfacial Effects on Lithium Superoxide Disproportionation in Li-O 2 Batteries
journal, January 2015

  • Zhai, Dengyun; Lau, Kah Chun; Wang, Hsien-Hau
  • Nano Letters, Vol. 15, Issue 2
  • DOI: 10.1021/nl503943z

Adsorption of oxygen on Pt(111)
journal, December 1982


Synthetic oxygen carriers related to biological systems
journal, April 1979

  • Jones, Robert D.; Summerville, David A.; Basolo, Fred.
  • Chemical Reviews, Vol. 79, Issue 2
  • DOI: 10.1021/cr60318a002

Near Neutrality of an Oxygen Molecule Adsorbed on a Pt(111) Surface
journal, September 2008


Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions
journal, August 2010

  • Cabana, Jordi; Monconduit, Laure; Larcher, Dominique
  • Advanced Materials, Vol. 22, Issue 35
  • DOI: 10.1002/adma.201000717

A Facile Mechanism for Recharging Li2O2 in Li–O2 Batteries
journal, August 2013

  • Kang, ShinYoung; Mo, Yifei; Ong, Shyue Ping
  • Chemistry of Materials, Vol. 25, Issue 16, p. 3328-3336
  • DOI: 10.1021/cm401720n

Rechargeable Lithium/TEGDME-LiPF[sub 6]∕O[sub 2] Battery
journal, January 2011

  • Laoire, Cormac Ó; Mukerjee, Sanjeev; Plichta, Edward J.
  • Journal of The Electrochemical Society, Vol. 158, Issue 3
  • DOI: 10.1149/1.3531981

Influence of Nonaqueous Solvents on the Electrochemistry of Oxygen in the Rechargeable Lithium−Air Battery
journal, April 2010

  • Laoire, Cormac O.; Mukerjee, Sanjeev; Abraham, K. M.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 19
  • DOI: 10.1021/jp102019y

The Influence of Catalysts on Discharge and Charge Voltages of Rechargeable Li–Oxygen Batteries
journal, January 2010

  • Lu, Yi-Chun; Gasteiger, Hubert A.; Parent, Michael C.
  • Electrochemical and Solid-State Letters, Vol. 13, Issue 6, p. A69-A72
  • DOI: 10.1149/1.3363047

Slurryless Li 2 S/Reduced Graphene Oxide Cathode Paper for High-Performance Lithium Sulfur Battery
journal, February 2015


A New Sealed Lithium-Peroxide Battery with a Co-Doped Li2O Cathode in a Superconcentrated Lithium Bis(fluorosulfonyl)amide Electrolyte
journal, July 2014

  • Okuoka, Shin-ichi; Ogasawara, Yoshiyuki; Suga, Yosuke
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep05684

Glass Transition Dynamics and Surface Layer Mobility in Unentangled Polystyrene Films
journal, June 2010


Enhanced mobility of confined polymers
journal, October 2007

  • Shin, Kyusoon; Obukhov, Sergei; Chen, Jiun-Tai
  • Nature Materials, Vol. 6, Issue 12
  • DOI: 10.1038/nmat2031

The distribution of glass-transition temperatures in nanoscopically confined glass formers
journal, September 2003

  • Ellison, Christopher J.; Torkelson, John M.
  • Nature Materials, Vol. 2, Issue 10
  • DOI: 10.1038/nmat980

The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li–O2 batteries
journal, November 2014

  • Johnson, Lee; Li, Chunmei; Liu, Zheng
  • Nature Chemistry, Vol. 6, Issue 12
  • DOI: 10.1038/nchem.2101

Raman Evidence for Late Stage Disproportionation in a Li–O2 Battery
journal, July 2014

  • Zhai, Dengyun; Wang, Hsien-Hau; Lau, Kah Chun
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 15, p. 2705-2710
  • DOI: 10.1021/jz501323n

Size-dependent melting point depression of nanostructures: Nanocalorimetric measurements
journal, October 2000


Density Functional Investigation of the Thermodynamic Stability of Lithium Oxide Bulk Crystalline Structures as a Function of Oxygen Pressure
journal, November 2011

  • Lau, Kah Chun; Curtiss, Larry A.; Greeley, Jeffrey
  • The Journal of Physical Chemistry C, Vol. 115, Issue 47, p. 23625-23633
  • DOI: 10.1021/jp206796h

Overpotential-Dependent Phase Transformation Pathways in Lithium Iron Phosphate Battery Electrodes
journal, November 2010

  • Kao, Yu-Hua; Tang, Ming; Meethong, Nonglak
  • Chemistry of Materials, Vol. 22, Issue 21
  • DOI: 10.1021/cm101698b

High-rate aluminium yolk-shell nanoparticle anode for Li-ion battery with long cycle life and ultrahigh capacity
journal, August 2015

  • Li, Sa; Niu, Junjie; Zhao, Yu Cheng
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8872

Computational Study of the Mechanisms of Superoxide-Induced Decomposition of Organic Carbonate-Based Electrolytes
journal, February 2011

  • Bryantsev, Vyacheslav S.; Blanco, Mario
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 5
  • DOI: 10.1021/jz1016526

Reactions in the Rechargeable Lithium–O 2 Battery with Alkyl Carbonate Electrolytes
journal, May 2011

  • Freunberger, Stefan A.; Chen, Yuhui; Peng, Zhangquan
  • Journal of the American Chemical Society, Vol. 133, Issue 20
  • DOI: 10.1021/ja2021747

New Nanostructured Li2S/Silicon Rechargeable Battery with High Specific Energy
journal, April 2010

  • Yang, Yuan; McDowell, Matthew T.; Jackson, Ariel
  • Nano Letters, Vol. 10, Issue 4, p. 1486-1491
  • DOI: 10.1021/nl100504q