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Title: Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen

Abstract

Non-aqueous lithium-oxygen batteries cycle by forming lithium peroxide during discharge and oxidizing it during recharge. The significant problem of oxidizing the solid insulating lithium peroxide can greatly be facilitated by incorporating redox mediators that shuttle electron-holes between the porous substrate and lithium peroxide. Redox mediator stability is thus key for energy efficiency, reversibility, and cycle life. However, the gradual deactivation of redox mediators during repeated cycling has not conclusively been explained. Here, we show that organic redox mediators are predominantly decomposed by singlet oxygen that forms during cycling. Their reaction with superoxide, previously assumed to mainly trigger their degradation, peroxide, and dioxygen, is orders of magnitude slower in comparison. The reduced form of the mediator is markedly more reactive towards singlet oxygen than the oxidized form, from which we derive reaction mechanisms supported by density functional theory calculations. Redox mediators must thus be designed for stability against singlet oxygen.

Authors:
 [1];  [1];  [2];  [2];  [1];  [2];  [3];  [3];  [4];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Hanyang Univ., Seoul (Republic of Korea)
  2. Graz Univ. of Technology, Graz (Austria)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Korea Inst. of Science and Technology, Seoul (Republic of Korea)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Korea Institute of Energy Technology Evaluation and Planning (KETEP); National Research Foundation of Korea (NRF); European Research Council (ERC); Austrian Science Fund (FWF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1505763
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

Kwak, Won -Jin, Kim, Hun, Petit, Yann K., Leypold, Christian, Nguyen, Trung Thien, Mahne, Nika, Redfern, Paul, Curtiss, Larry A., Jung, Hun -Gi, Borisov, Sergey M., Freunberger, Stefan A., and Sun, Yang -Kook. Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen. United States: N. p., 2019. Web. doi:10.1038/s41467-019-09399-0.
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Kwak, Won -Jin, Kim, Hun, Petit, Yann K., Leypold, Christian, Nguyen, Trung Thien, Mahne, Nika, Redfern, Paul, Curtiss, Larry A., Jung, Hun -Gi, Borisov, Sergey M., Freunberger, Stefan A., & Sun, Yang -Kook. Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen. United States. doi:10.1038/s41467-019-09399-0.
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Kwak, Won -Jin, Kim, Hun, Petit, Yann K., Leypold, Christian, Nguyen, Trung Thien, Mahne, Nika, Redfern, Paul, Curtiss, Larry A., Jung, Hun -Gi, Borisov, Sergey M., Freunberger, Stefan A., and Sun, Yang -Kook. Tue . "Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen". United States. doi:10.1038/s41467-019-09399-0. https://www.osti.gov/servlets/purl/1505763.
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@article{osti_1505763,
title = {Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen},
author = {Kwak, Won -Jin and Kim, Hun and Petit, Yann K. and Leypold, Christian and Nguyen, Trung Thien and Mahne, Nika and Redfern, Paul and Curtiss, Larry A. and Jung, Hun -Gi and Borisov, Sergey M. and Freunberger, Stefan A. and Sun, Yang -Kook},
abstractNote = {Non-aqueous lithium-oxygen batteries cycle by forming lithium peroxide during discharge and oxidizing it during recharge. The significant problem of oxidizing the solid insulating lithium peroxide can greatly be facilitated by incorporating redox mediators that shuttle electron-holes between the porous substrate and lithium peroxide. Redox mediator stability is thus key for energy efficiency, reversibility, and cycle life. However, the gradual deactivation of redox mediators during repeated cycling has not conclusively been explained. Here, we show that organic redox mediators are predominantly decomposed by singlet oxygen that forms during cycling. Their reaction with superoxide, previously assumed to mainly trigger their degradation, peroxide, and dioxygen, is orders of magnitude slower in comparison. The reduced form of the mediator is markedly more reactive towards singlet oxygen than the oxidized form, from which we derive reaction mechanisms supported by density functional theory calculations. Redox mediators must thus be designed for stability against singlet oxygen.},
doi = {10.1038/s41467-019-09399-0},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {3}
}
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DOI:  10.1038/s41467-019-09399-0
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Works referenced in this record:

Photosensitized singlet oxygen and its applications
journal, November 2002

Mechanism and performance of lithium–oxygen batteries – a perspective
journal, January 2017

  • Mahne, Nika; Fontaine, Olivier; Thotiyl, Musthafa Ottakam
  • Chemical Science, Vol. 8, Issue 10
  • DOI: 10.1039/C7SC02519J

Screening for Superoxide Reactivity in Li-O 2 Batteries: Effect on Li 2 O 2 /LiOH Crystallization
journal, February 2012

  • Black, Robert; Oh, Si Hyoung; Lee, Jin-Hyon
  • Journal of the American Chemical Society, Vol. 134, Issue 6
  • DOI: 10.1021/ja2111543

Advances in understanding mechanisms underpinning lithium–air batteries
journal, September 2016

A Viewpoint on Heterogeneous Electrocatalysis and Redox Mediation in Nonaqueous Li-O 2 Batteries
journal, December 2016

The Carbon Electrode in Nonaqueous Li–O2 Cells
journal, December 2012

  • Ottakam Thotiyl, Muhammed M.; Freunberger, Stefan A.; Peng, Zhangquan
  • Journal of the American Chemical Society, Vol. 135, Issue 1, p. 494-500
  • DOI: 10.1021/ja310258x

Singlet Oxygen Formation during the Charging Process of an Aprotic Lithium-Oxygen Battery
journal, May 2016

  • Wandt, Johannes; Jakes, Peter; Granwehr, Josef
  • Angewandte Chemie International Edition, Vol. 55, Issue 24
  • DOI: 10.1002/anie.201602142

Controversial Topics on Lithium Superoxide in Li–O 2 Batteries
journal, November 2017

Reversible Binding of Oxygen to Aromatic Compounds
journal, September 2003

  • Aubry, Jean-Marie; Pierlot, Christel; Rigaudy, Jean
  • Accounts of Chemical Research, Vol. 36, Issue 9
  • DOI: 10.1021/ar010086g

A Soft Chemistry Approach to Coating of LiFePO4 with a Conducting Polymer
journal, June 2011

  • Lepage, David; Michot, Christophe; Liang, Guoxian
  • Angewandte Chemie International Edition, Vol. 50, Issue 30
  • DOI: 10.1002/anie.201101661

Reversibility of Noble Metal-Catalyzed Aprotic Li-O 2 Batteries
journal, November 2015

Mechanistic insights for the development of Li–O 2 battery materials: addressing Li 2 O 2 conductivity limitations and electrolyte and cathode instabilities
journal, January 2015

  • McCloskey, Bryan D.; Burke, Colin M.; Nichols, Jessica E.
  • Chemical Communications, Vol. 51, Issue 64
  • DOI: 10.1039/C5CC04620C

Theoretical Prediction of a Perepoxide Intermediate for the Reaction of Singlet Oxygen with trans -Cyclooctene Contrasts with the Two-Step No-Intermediate Ene Reaction for Acyclic Alkenes
journal, November 2008

  • Leach, Andrew G.; Houk, K. N.; Foote, Christopher S.
  • The Journal of Organic Chemistry, Vol. 73, Issue 21
  • DOI: 10.1021/jo8016154

A Moisture- and Oxygen-Impermeable Separator for Aprotic Li-O 2 Batteries
journal, February 2016

  • Kim, Byung Gon; Kim, Joo-Seong; Min, Jaeyun
  • Advanced Functional Materials, Vol. 26, Issue 11
  • DOI: 10.1002/adfm.201504437

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

Singlet oxygen: there is indeed something new under the sun
journal, January 2010

  • Ogilby, Peter R.
  • Chemical Society Reviews, Vol. 39, Issue 8
  • DOI: 10.1039/b926014p

Optimized Bicompartment Two Solution Cells for Effective and Stable Operation of Li-O 2 Batteries
journal, August 2017

  • Kwak, Won-Jin; Jung, Hun-Gi; Aurbach, Doron
  • Advanced Energy Materials, Vol. 7, Issue 21
  • DOI: 10.1002/aenm.201701232

The Role of Catalysts and Peroxide Oxidation in Lithium-Oxygen Batteries
journal, November 2012

  • Black, Robert; Lee, Jin-Hyon; Adams, Brian
  • Angewandte Chemie International Edition, Vol. 52, Issue 1, p. 392-396
  • DOI: 10.1002/anie.201205354

Bifunctional Redox Mediator Supported by an Anionic Surfactant for Long-Cycle Li–O 2 Batteries
journal, October 2017

Mechanism of Ene Reactions of Singlet Oxygen. A Two-Step No-Intermediate Mechanism
journal, February 2003

  • Singleton, Daniel A.; Hang, Chao; Szymanski, Michael J.
  • Journal of the American Chemical Society, Vol. 125, Issue 5
  • DOI: 10.1021/ja027225p

Sustainable Redox Mediation for Lithium-Oxygen Batteries by a Composite Protective Layer on the Lithium-Metal Anode
journal, December 2015

  • Lee, Dong Jin; Lee, Hongkyung; Kim, Yun-Jung
  • Advanced Materials, Vol. 28, Issue 5
  • DOI: 10.1002/adma.201503169

Review—A Comparative Evaluation of Redox Mediators for Li-O 2 Batteries: A Critical Review
journal, January 2018

  • Kwak, Won-Jin; Kim, Hun; Jung, Hun-Gi
  • Journal of The Electrochemical Society, Vol. 165, Issue 10
  • DOI: 10.1149/2.0901810jes

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

Intermediates in the ene reactions of singlet oxygen and N-phenyl-1,2,4-triazoline-3,5-dione with olefins
journal, April 1990

  • Orfanopoulos, M.; Smonou, I.; Foote, Christopher S.
  • Journal of the American Chemical Society, Vol. 112, Issue 9
  • DOI: 10.1021/ja00165a053

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen
journal, April 2018

  • Mahne, Nika; Renfrew, Sara E.; McCloskey, Bryan D.
  • Angewandte Chemie International Edition, Vol. 57, Issue 19
  • DOI: 10.1002/anie.201802277

Combining Accurate O 2 and Li 2 O 2 Assays to Separate Discharge and Charge Stability Limitations in Nonaqueous Li–O 2 Batteries
journal, August 2013

  • McCloskey, Bryan D.; Valery, Alexia; Luntz, Alan C.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 17
  • DOI: 10.1021/jz401659f

Lithium–oxygen batteries: At a crossroads?
journal, December 2017

  • Vegge, Tejs; Garcia-Lastra, Juan Maria; Siegel, Donald J.
  • Current Opinion in Electrochemistry, Vol. 6, Issue 1
  • DOI: 10.1016/j.coelec.2017.10.014

Chemistry of singlet oxygen. 35. Nature of intermediates in the photooxygenation of sulfides
journal, September 1981

  • Gu, Chee-Liang; Foote, Christopher S.; Kacher, Mark L.
  • Journal of the American Chemical Society, Vol. 103, Issue 19
  • DOI: 10.1021/ja00409a073

Charging a Li–O2 battery using a redox mediator
journal, May 2013

  • Chen, Yuhui; Freunberger, Stefan A.; Peng, Zhangquan
  • Nature Chemistry, Vol. 5, Issue 6
  • DOI: 10.1038/nchem.1646

A Highly Active Low Voltage Redox Mediator for Enhanced Rechargeability of Lithium–Oxygen Batteries
journal, November 2015

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Redox Mediators for Li-O 2 Batteries: Status and Perspectives
journal, November 2017

Chemi- and Bioluminescence of Cyclic Peroxides
journal, March 2018

A Highly Active Oxygen Evolution Catalyst for Lithium-Oxygen Batteries Enabled by High-Surface-Energy Facets
journal, August 2018

Rational design of redox mediators for advanced Li–O2 batteries
journal, May 2016

Li–O 2 Cell with LiI(3-hydroxypropionitrile) 2 as a Redox Mediator: Insight into the Working Mechanism of I – during Charge in Anhydrous Systems
journal, August 2017

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries
journal, March 2017

Towards a Stable Organic Electrolyte for the Lithium Oxygen Battery
journal, August 2014

  • Adams, Brian D.; Black, Robert; Williams, Zack
  • Advanced Energy Materials, Vol. 5, Issue 1
  • DOI: 10.1002/aenm.201400867

On the Efficacy of Electrocatalysis in Nonaqueous Li–O 2 Batteries
journal, November 2011

  • McCloskey, Bryan D.; Scheffler, Rouven; Speidel, Angela
  • Journal of the American Chemical Society, Vol. 133, Issue 45
  • DOI: 10.1021/ja207229n

New NIR-emitting complexes of platinum(II) and palladium(II) with fluorinated benzoporphyrins
journal, January 2009

How To Improve Capacity and Cycling Stability for Next Generation Li–O 2 Batteries: Approach with a Solid Electrolyte and Elevated Redox Mediator Concentrations
journal, March 2016

  • Bergner, Benjamin J.; Busche, Martin R.; Pinedo, Ricardo
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 12
  • DOI: 10.1021/acsami.5b10979

Thermolysis of tetramethoxy- and p-dioxenedioxetanes. Kinetic parameters, chemiluminescence, and yields of excited products
journal, March 1976

  • Wilson, Therese; Golan, David E.; Harris, M. Scott
  • Journal of the American Chemical Society, Vol. 98, Issue 5
  • DOI: 10.1021/ja00421a005

A Solution-Phase Bifunctional Catalyst for Lithium–Oxygen Batteries
journal, June 2014

  • Sun, Dan; Shen, Yue; Zhang, Wang
  • Journal of the American Chemical Society, Vol. 136, Issue 25
  • DOI: 10.1021/ja501877e

Kinetics of lithium peroxide oxidation by redox mediators and consequences for the lithium–oxygen cell
journal, February 2018

Nature of Li 2 O 2 Oxidation in a Li–O 2 Battery Revealed by Operando X-ray Diffraction
journal, November 2014

  • Ganapathy, Swapna; Adams, Brian D.; Stenou, Georgiana
  • Journal of the American Chemical Society, Vol. 136, Issue 46
  • DOI: 10.1021/ja508794r

A Comprehensive Modeling Study of n-Heptane Oxidation
journal, July 1998

Lithium–oxygen batteries: bridging mechanistic understanding and battery performance
journal, January 2013

  • Lu, Yi-Chun; Gallant, Betar M.; Kwabi, David G.
  • Energy & Environmental Science, Vol. 6, Issue 3
  • DOI: 10.1039/c3ee23966g

Li–O 2 Battery Degradation by Lithium Peroxide (Li 2 O 2 ): A Model Study
journal, December 2012

  • Younesi, Reza; Hahlin, Maria; Björefors, Fredrik
  • Chemistry of Materials, Vol. 25, Issue 1
  • DOI: 10.1021/cm303226g

Surface-Mediated Solvent Decomposition in Li–Air Batteries: Impact of Peroxide and Superoxide Surface Terminations
journal, April 2015

  • Kumar, Nitin; Radin, Maxwell D.; Wood, Brandon C.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 17
  • DOI: 10.1021/acs.jpcc.5b00256

Reaction of Organic Sulfides with Singlet Oxygen. A Revised Mechanism
journal, May 1998

  • Jensen, Frank; Greer, Alexander; Clennan, Edward L.
  • Journal of the American Chemical Society, Vol. 120, Issue 18
  • DOI: 10.1021/ja973782d

Predicting Autoxidation Stability of Ether- and Amide-Based Electrolyte Solvents for Li–Air Batteries
journal, June 2012

  • Bryantsev, Vyacheslav S.; Faglioni, Francesco
  • The Journal of Physical Chemistry A, Vol. 116, Issue 26
  • DOI: 10.1021/jp301537w

Predicting Solvent Stability in Aprotic Electrolyte Li–Air Batteries: Nucleophilic Substitution by the Superoxide Anion Radical (O 2 •– )
journal, November 2011

  • Bryantsev, Vyacheslav S.; Giordani, Vincent; Walker, Wesley
  • The Journal of Physical Chemistry A, Vol. 115, Issue 44
  • DOI: 10.1021/jp2073914

Poly(vinylidene fluoride) (PVDF) Binder Degradation in Li–O 2 Batteries: A Consideration for the Characterization of Lithium Superoxide
journal, February 2017

  • Papp, Joseph K.; Forster, Jason D.; Burke, Colin M.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 6
  • DOI: 10.1021/acs.jpclett.7b00040

Degradation of LiTfO/TEGME and LiTfO/DME Electrolytes in Li-O 2 Batteries
journal, January 2018

  • Carboni, Marco; Marrani, Andrea Giacomo; Spezia, Riccardo
  • Journal of The Electrochemical Society, Vol. 165, Issue 2
  • DOI: 10.1149/2.0331802jes

LiO 2 : Cryosynthesis and Chemical/Electrochemical Reactivities
journal, May 2017

TEMPO: A Mobile Catalyst for Rechargeable Li-O 2 Batteries
journal, October 2014

  • Bergner, Benjamin J.; Schürmann, Adrian; Peppler, Klaus
  • Journal of the American Chemical Society, Vol. 136, Issue 42
  • DOI: 10.1021/ja508400m

Chemistry of singlet oxygen. XIV. Reactive intermediate in sulfide photooxidation
journal, July 1971

  • Foote, Christopher S.; Peters, John W.
  • Journal of the American Chemical Society, Vol. 93, Issue 15
  • DOI: 10.1021/ja00744a055

How Dopants Can Enhance Charge Transport in Li 2 O 2
journal, January 2015

  • Radin, Maxwell D.; Monroe, Charles W.; Siegel, Donald J.
  • Chemistry of Materials, Vol. 27, Issue 3
  • DOI: 10.1021/cm503874c

Singlet Oxygen during Cycling of the Aprotic Sodium-O 2 Battery
journal, November 2017

  • Schafzahl, Lukas; Mahne, Nika; Schafzahl, Bettina
  • Angewandte Chemie International Edition, Vol. 56, Issue 49
  • DOI: 10.1002/anie.201709351
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