Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen
Abstract
Abstract Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O 2 batteries, and are believed to form and decompose reversibly in metal‐O 2 /CO 2 cells. In these cathodes, Li 2 CO 3 decomposes to CO 2 when exposed to potentials above 3.8 V vs. Li/Li + . However, O 2 evolution, as would be expected according to the decomposition reaction 2 Li 2 CO 3 →4 Li + +4 e − +2 CO 2 +O 2 , is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen ( 1 O 2 ) forms upon oxidizing Li 2 CO 3 in an aprotic electrolyte and therefore does not evolve as O 2 . These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding 1 O 2 in metal‐O 2 batteries, question the possibility of a reversible metal‐O 2 /CO 2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li 2 CO 3 .
- Authors:
-
[1];
[2];
[2];
[1]
- Institute for Chemistry and Technology of Materials Graz University of Technology Stremayrgasse 9 8010 Graz Austria
- Energy Storage and Distributed Resources Division Lawrence Berkeley National Laboratory, Department of Chemical and Biomolecular Engineering University of California – Berkeley Berkeley CA 94720 USA
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1433266
- Alternate Identifier(s):
- OSTI ID: 1433267; OSTI ID: 1460317
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition) Journal Volume: 57 Journal Issue: 19; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; electrochemistry; lithium batteries; lithium carbonate; reaction mechanisms; singlet oxygen
Citation Formats
Mahne, Nika, Renfrew, Sara E., McCloskey, Bryan D., and Freunberger, Stefan A. Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen. Germany: N. p., 2018.
Web. doi:10.1002/anie.201802277.
Mahne, Nika, Renfrew, Sara E., McCloskey, Bryan D., & Freunberger, Stefan A. Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen. Germany. https://doi.org/10.1002/anie.201802277
Mahne, Nika, Renfrew, Sara E., McCloskey, Bryan D., and Freunberger, Stefan A. Sat .
"Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen". Germany. https://doi.org/10.1002/anie.201802277.
@article{osti_1433266,
title = {Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen},
author = {Mahne, Nika and Renfrew, Sara E. and McCloskey, Bryan D. and Freunberger, Stefan A.},
abstractNote = {Abstract Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O 2 batteries, and are believed to form and decompose reversibly in metal‐O 2 /CO 2 cells. In these cathodes, Li 2 CO 3 decomposes to CO 2 when exposed to potentials above 3.8 V vs. Li/Li + . However, O 2 evolution, as would be expected according to the decomposition reaction 2 Li 2 CO 3 →4 Li + +4 e − +2 CO 2 +O 2 , is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen ( 1 O 2 ) forms upon oxidizing Li 2 CO 3 in an aprotic electrolyte and therefore does not evolve as O 2 . These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding 1 O 2 in metal‐O 2 batteries, question the possibility of a reversible metal‐O 2 /CO 2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li 2 CO 3 .},
doi = {10.1002/anie.201802277},
journal = {Angewandte Chemie (International Edition)},
number = 19,
volume = 57,
place = {Germany},
year = {Sat Apr 14 00:00:00 EDT 2018},
month = {Sat Apr 14 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/anie.201802277
https://doi.org/10.1002/anie.201802277
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 160 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013
- Sathiya, M.; Rousse, G.; Ramesha, K.
- Nature Materials, Vol. 12, Issue 9
A Molten Salt Lithium–Oxygen Battery
journal, February 2016
- Giordani, Vincent; Tozier, Dylan; Tan, Hongjin
- Journal of the American Chemical Society, Vol. 138, Issue 8
Electro-Oxidation of Carbonate in Aqueous Solution on a Platinum Rotating Ring Disk Electrode
journal, October 2005
- Zhang, Jiujun; Oloman, Colin W.
- Journal of Applied Electrochemistry, Vol. 35, Issue 10
Achilles’ Heel of Lithium-Air Batteries: Lithium Carbonate
journal, March 2018
- Zhao, Zhiwei; Huang, Jun; Peng, Zhangquan
- Angewandte Chemie International Edition, Vol. 57, Issue 15
Positive electrode materials with high operating voltage for lithium batteries: LiCryMn2 − yO4 (0 ≤ y ≤ 1)
journal, November 1995
- Sigala, C.; Guyomard, D.; Verbaere, A.
- Solid State Ionics, Vol. 81, Issue 3-4
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016
- Luo, Kun; Roberts, Matthew R.; Hao, Rong
- Nature Chemistry, Vol. 8, Issue 7
Advances in understanding mechanisms underpinning lithium–air batteries
journal, September 2016
- Aurbach, Doron; McCloskey, Bryan D.; Nazar, Linda F.
- Nature Energy, Vol. 1, Issue 9
Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors
journal, September 2012
- Choi, Nam-Soon; Chen, Zonghai; Freunberger, Stefan A.
- Angewandte Chemie International Edition, Vol. 51, Issue 40
Exploring the electrochemical reaction mechanism of carbonate oxidation in Li–air/CO 2 battery through tracing missing oxygen
journal, January 2016
- Yang, Sixie; He, Ping; Zhou, Haoshen
- Energy & Environmental Science, Vol. 9, Issue 5
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014
- Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
- Nature Communications, Vol. 5, Issue 1
Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries
journal, March 2017
- Mahne, Nika; Schafzahl, Bettina; Leypold, Christian
- Nature Energy, Vol. 2, Issue 5
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
Mechanistic Insights into Catalyst-Assisted Nonaqueous Oxygen Evolution Reaction in Lithium–Oxygen Batteries
journal, March 2016
- Wang, Yu; Liang, Zhuojian; Zou, Qingli
- The Journal of Physical Chemistry C, Vol. 120, Issue 12
Synthesis, Structure, and Electrochemical Behavior of Li[Ni[sub x]Li[sub 1/3−2x/3]Mn[sub 2/3−x/3]]O[sub 2]
journal, January 2002
- Lu, Zhonghua; Beaulieu, L. Y.; Donaberger, R. A.
- Journal of The Electrochemical Society, Vol. 149, Issue 6
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
Monodispersed Ru Nanoparticles Functionalized Graphene Nanosheets as Efficient Cathode Catalysts for O 2 -Assisted Li–CO 2 Battery
journal, December 2017
- Wang, Liangjun; Dai, Wenrui; Ma, Lipo
- ACS Omega, Vol. 2, Issue 12
Singlet oxygen: there is indeed something new under the sun
journal, January 2010
- Ogilby, Peter R.
- Chemical Society Reviews, Vol. 39, Issue 8
Implications of CO 2 Contamination in Rechargeable Nonaqueous Li–O 2 Batteries
journal, December 2012
- Gowda, S. R.; Brunet, A.; Wallraff, G. M.
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 2
Singulett-Sauerstoff in der aprotischen Natrium-O 2 -Batterie
journal, November 2017
- Schafzahl, Lukas; Mahne, Nika; Schafzahl, Bettina
- Angewandte Chemie, Vol. 129, Issue 49
Alkali-metal peroxocarbonates, M 2 [CO 3 ]·nH 2 O 2 , M 2 [C 2 O 6 ], M[HCO 4 ]·nH 2 O, and Li 2 [CO 4 ]·H 2 O
journal, January 1980
- Jones, D. Philip; Griffith, William P.
- J. Chem. Soc., Dalton Trans., Issue 12
Singlet Oxygen-Induced Photodegradation of the Polymers and Dyes in Optical Sensing Materials and the Effect of Stabilizers on These Processes
journal, September 2013
- Enko, Barbara; Borisov, Sergey M.; Regensburger, Johannes
- The Journal of Physical Chemistry A, Vol. 117, Issue 36
Synthesis and Electrochemistry of LiNi[sub x]Mn[sub 2−x]O[sub 4]
journal, January 1997
- Zhong, Qiming
- Journal of The Electrochemical Society, Vol. 144, Issue 1
Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries
journal, January 2007
- Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S.
- Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125
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
- Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek
- Journal of the American Chemical Society, Vol. 133, Issue 12
Intrinsic Barrier to Electrochemically Decompose Li 2 CO 3 and LiOH
journal, November 2014
- Ling, Chen; Zhang, Ruigang; Takechi, Kensuke
- The Journal of Physical Chemistry C, Vol. 118, Issue 46
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
Li 2 CO 3 : Die Achillesferse von Lithium-Luft-Batterien
journal, March 2018
- Zhao, Zhiwei; Huang, Jun; Peng, Zhangquan
- Angewandte Chemie, Vol. 130, Issue 15
Lithiumbatterien und elektrische Doppelschichtkondensatoren: aktuelle Herausforderungen
journal, September 2012
- Choi, Nam-Soon; Chen, Zonghai; Freunberger, Stefan A.
- Angewandte Chemie, Vol. 124, Issue 40
Singlet Molecular Oxygen Generated from Lipid Hydroperoxides by the Russell Mechanism: Studies Using 18 O-Labeled Linoleic Acid Hydroperoxide and Monomol Light Emission Measurements
journal, May 2003
- Miyamoto, Sayuri; Martinez, Glaucia R.; Medeiros, Marisa H. G.
- Journal of the American Chemical Society, Vol. 125, Issue 20
Singlet Oxygen Formation during the Charging Process of an Aprotic Lithium-Oxygen Battery
journal, April 2016
- Wandt, Johannes; Jakes, Peter; Granwehr, Josef
- Angewandte Chemie, Vol. 128, Issue 24
Toward a Lithium–“Air” Battery: The Effect of CO 2 on the Chemistry of a Lithium–Oxygen Cell
journal, June 2013
- Lim, Hyung-Kyu; Lim, Hee-Dae; Park, Kyu-Young
- Journal of the American Chemical Society, Vol. 135, Issue 26
Residual Lithium Carbonate Predominantly Accounts for First Cycle CO 2 and CO Outgassing of Li-Stoichiometric and Li-Rich Layered Transition-Metal Oxides
journal, November 2017
- Renfrew, Sara E.; McCloskey, Bryan D.
- Journal of the American Chemical Society, Vol. 139, Issue 49
Sacrificial salts: Compensating the initial charge irreversibility in lithium batteries
journal, October 2010
- Shanmukaraj, Devaraj; Grugeon, Sylvie; Laruelle, Stéphane
- Electrochemistry Communications, Vol. 12, Issue 10
The Formation Mechanism of Fluorescent Metal Complexes at the Li x Ni 0.5 Mn 1.5 O 4−δ /Carbonate Ester Electrolyte Interface
journal, March 2015
- Jarry, Angélique; Gottis, Sébastien; Yu, Young-Sang
- Journal of the American Chemical Society, Vol. 137, Issue 10
Promise and reality of post-lithium-ion batteries with high energy densities
journal, March 2016
- Choi, Jang Wook; Aurbach, Doron
- Nature Reviews Materials, Vol. 1, Issue 4
Rechargeability of Li–air cathodes pre-filled with discharge products using an ether-based electrolyte solution: implications for cycle-life of Li–air cells
journal, January 2013
- Meini, Stefano; Tsiouvaras, Nikolaos; Schwenke, K. Uta
- Physical Chemistry Chemical Physics, Vol. 15, Issue 27
Correlation between dissolution behavior and electrochemical cycling performance for LiNi1/3Co1/3Mn1/3O2-based cells
journal, June 2012
- Zheng, Honghe; Sun, Qingna; Liu, Gao
- Journal of Power Sources, Vol. 207
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
On the incompatibility of lithium–O 2 battery technology with CO 2
journal, January 2017
- Zhang, Shiyu; Nava, Matthew J.; Chow, Gary K.
- Chemical Science, Vol. 8, Issue 9