Role of LiCoO2 Surface Terminations in Oxygen Reduction and Evolution Kinetics

Han, Binghong; Qian, Danna; Risch, Marcel; Chi, Miaofang; Meng, Ying Shirley; Yang, Shao-horn

doi:10.1021/acs.jpclett.5b00332

Title: Role of LiCoO₂ Surface Terminations in Oxygen Reduction and Evolution Kinetics

Journal Article · Sun Mar 22 00:00:00 EDT 2015 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.5b00332· OSTI ID:1265784

Han, Binghong ^[1]; Qian, Danna ^[2]; Risch, Marcel ^[1]; Chi, Miaofang ^[2]; Meng, Ying Shirley ^[3]; Yang, Shao-horn ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of California, San Diego, CA (United States)

We studied oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO₂ nanorods with sizes in the range from 9 to 40 nm in alkaline solution. We also terminated the sides of these nanorods with low-index surfaces such as (003), while the tips were terminated largely with high-index surfaces such as (104), as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co³⁺ prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co³⁺. Finally, we correlated the electronic and atomic structure to higher specific ORR and OER activities at the tips as compared to the sides, which was accompanied by more facile redox of Co^2+/3+ and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition-metal oxides on the ORR and OER activity.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; EE0000458; DMR 08-019762

OSTI ID:: 1265784

Alternate ID(s):: OSTI ID: 1279418

Journal Information:: Journal of Physical Chemistry Letters, Vol. 6, Issue 8; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 51 works

Citation information provided by
Web of Science

References (25)

Hydrogen Cars: Fad or the Future? Service, R. F. Science, Vol. 324, Issue 5932 https://doi.org/10.1126/science.324_1257	journal	June 2009
Erratum: Powering the planet with solar fuel Gray, Harry B. Nature Chemistry, Vol. 1, Issue 2 https://doi.org/10.1038/nchem.206	journal	May 2009
Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co²⁺ Kanan, M. W.; Nocera, D. G. Science, Vol. 321, Issue 5892, p. 1072-1075 https://doi.org/10.1126/science.1162018	journal	August 2008
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction McCrory, Charles C. L.; Jung, Suho; Peters, Jonas C. Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja407115p	journal	October 2013
Platinum−Gold Nanoparticles: A Highly Active Bifunctional Electrocatalyst for Rechargeable Lithium−Air Batteries Lu, Yi-Chun; Xu, Zhichuan; Gasteiger, Hubert A. Journal of the American Chemical Society, Vol. 132, Issue 35, p. 12170-12171 https://doi.org/10.1021/ja1036572	journal	September 2010
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
The Nature of Lithium Battery Materials under Oxygen Evolution Reaction Conditions Lee, Seung Woo; Carlton, Christopher; Risch, Marcel Journal of the American Chemical Society, Vol. 134, Issue 41 https://doi.org/10.1021/ja307814j	journal	October 2012
La _0.8 Sr _0.2 MnO _3−δ Decorated with Ba _0.5 Sr _0.5 Co _0.8 Fe _0.2 O _3−δ : A Bifunctional Surface for Oxygen Electrocatalysis with Enhanced Stability and Activity Risch, Marcel; Stoerzinger, Kelsey A.; Maruyama, Shingo Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja5009954	journal	February 2014
Oxygen electrocatalysis on (001)-oriented manganese perovskite films: Mn valency and charge transfer at the nanoscale Stoerzinger, Kelsey A.; Risch, Marcel; Suntivich, Jin Energy & Environmental Science, Vol. 6, Issue 5 https://doi.org/10.1039/c3ee40321a	journal	January 2013
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles Suntivich, J.; May, K. J.; Gasteiger, H. A. Science, Vol. 334, Issue 6061 https://doi.org/10.1126/science.1212858	journal	October 2011
Low-cost Oxygen Electrode Material Meadowcroft, D. B. Nature, Vol. 226, Issue 5248 https://doi.org/10.1038/226847a0	journal	May 1970
Electrocatalytic Measurement Methodology of Oxide Catalysts Using a Thin-Film Rotating Disk Electrode Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki Journal of The Electrochemical Society, Vol. 157, Issue 8 https://doi.org/10.1149/1.3456630	journal	January 2010
Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions Maiyalagan, Thandavarayan; Jarvis, Karalee A.; Therese, Soosairaj Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4949	journal	May 2014
Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki Nature Chemistry, Vol. 3, Issue 7, p. 546-550 https://doi.org/10.1038/nchem.1069	journal	June 2011
Estimating Hybridization of Transition Metal and Oxygen States in Perovskites from O K -edge X-ray Absorption Spectroscopy Suntivich, Jin; Hong, Wesley T.; Lee, Yueh-Lin The Journal of Physical Chemistry C, Vol. 118, Issue 4 https://doi.org/10.1021/jp410644j	journal	January 2014
Oxygen Evolution Activity and Stability of Ba ₆ Mn ₅ O ₁₆ , Sr ₄ Mn ₂ CoO ₉ , and Sr ₆ Co ₅ O ₁₅ : The Influence of Transition Metal Coordination Grimaud, Alexis; Carlton, Christopher E.; Risch, Marcel The Journal of Physical Chemistry C, Vol. 117, Issue 49 https://doi.org/10.1021/jp408585z	journal	November 2013
Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide Qian, Danna; Hinuma, Yoyo; Chen, Hailong Journal of the American Chemical Society, Vol. 134, Issue 14 https://doi.org/10.1021/ja300868e	journal	March 2012
Instability of Pt∕C Electrocatalysts in Proton Exchange Membrane Fuel Cells Ferreira, P. J.; la O’, G. J.; Shao-Horn, Y. Journal of The Electrochemical Society, Vol. 152, Issue 11 https://doi.org/10.1149/1.2050347	journal	January 2005
Water oxidation by amorphous cobalt-based oxides: in situ tracking of redox transitions and mode of catalysis Risch, Marcel; Ringleb, Franziska; Kohlhoff, Mike Energy & Environmental Science, Vol. 8, Issue 2 https://doi.org/10.1039/C4EE03004D	journal	January 2015
On the chemical state of Co oxide electrocatalysts during alkaline water splitting Friebel, Daniel; Bajdich, Michal; Yeo, Boon Siang Physical Chemistry Chemical Physics, Vol. 15, Issue 40 https://doi.org/10.1039/c3cp52981a	journal	January 2013
In Situ Co K-Edge X-Ray Absorption Fine Structure of Cobalt Hydroxide Film Electrodes in Alkaline Solutions Totir, Dana; Mo, Yibo; Kim, Sunghyun Journal of The Electrochemical Society, Vol. 147, Issue 12 https://doi.org/10.1149/1.1394107	journal	January 2000
Nickel–cobalt double hydroxides microspheres with hollow interior and hedgehog-like exterior structures for supercapacitors Tao, Yan; Zaijun, Li; Ruiyi, Li Journal of Materials Chemistry, Vol. 22, Issue 44 https://doi.org/10.1039/c2jm35263j	journal	January 2012
First In Situ Observation of the LiCoO ₂ Electrode/Electrolyte Interface by Total-Reflection X-ray Absorption Spectroscopy Takamatsu, Daiko; Koyama, Yukinori; Orikasa, Yuki Angewandte Chemie International Edition, Vol. 51, Issue 46 https://doi.org/10.1002/anie.201203910	journal	October 2012
Structural Requirements in Lithium Cobalt Oxides for the Catalytic Oxidation of Water Gardner, Graeme P.; Go, Yong Bok; Robinson, David M. Angewandte Chemie International Edition, Vol. 51, Issue 7 https://doi.org/10.1002/anie.201107625	journal	January 2012

Cited By (14)

Engineering electrocatalytic activity in nanosized perovskite cobaltite through surface spin-state transition Zhou, Shiming; Miao, Xianbing; Zhao, Xu Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11510	journal	May 2016
Atomic-Scale CoO _x Species in Metal-Organic Frameworks for Oxygen Evolution Reaction Dou, Shuo; Dong, Chung-Li; Hu, Zhe Advanced Functional Materials, Vol. 27, Issue 36 https://doi.org/10.1002/adfm.201702546	journal	August 2017
Spin state engineered Zn _x Co _3−x O ₄ as an efficient oxygen evolution electrocatalyst Ramsundar, Rani Mohan; Pillai, Vijayamohanan Kunjukrishna; Joy, Pattayil Alias Physical Chemistry Chemical Physics, Vol. 20, Issue 46 https://doi.org/10.1039/c8cp06641h	journal	January 2018
Unified structural motifs of the catalytically active state of Co(oxyhydr)oxides during the electrochemical oxygen evolution reaction Bergmann, Arno; Jones, Travis E.; Martinez Moreno, Elias Nature Catalysis, Vol. 1, Issue 9 https://doi.org/10.1038/s41929-018-0141-2	journal	September 2018
Boosting reversible oxygen electrocatalysis with enhanced interfacial pyridinic-N–Co bonding in cobalt oxide/mesoporous N-doped graphene hybrids Feng, Ting; Zhao, Xue-Ru; Dong, Cun-Ku Nanoscale, Vol. 10, Issue 47 https://doi.org/10.1039/c8nr07945e	journal	January 2018
Evidence that Crystal Facet Orientation Dictates Oxygen Evolution Intermediates on Rutile Manganese Oxide Kakizaki, Hirotaka; Ooka, Hideshi; Hayashi, Toru Advanced Functional Materials, Vol. 28, Issue 24 https://doi.org/10.1002/adfm.201706319	journal	February 2018
An Insight on the Electrocatalytic Mechanistic Study of Pristine Ni MOF (BTC) in Alkaline Medium for Enhanced OER and UOR Maruthapandian, Viruthasalam; Kumaraguru, Shanmugasundaram; Mohan, Subramanian ChemElectroChem, Vol. 5, Issue 19 https://doi.org/10.1002/celc.201800802	journal	July 2018
LiCoO2 particles used in Li-ion batteries induce primary mutagenicity in lung cells via their capacity to generate hydroxyl radicals Sironval, Violaine; Scagliarini, Vittoria; Murugadoss, Sivakumar Particle and Fibre Toxicology, Vol. 17, Issue 1 https://doi.org/10.1186/s12989-020-0338-9	journal	January 2020
Nanoscale structural oscillations in perovskite oxides induced by oxygen evolution Han, Binghong; Stoerzinger, Kelsey A.; Tileli, Vasiliki Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4764	journal	October 2016
π‐Conjugated Molecule Boosts Metal–Organic Frameworks as Efficient Oxygen Evolution Reaction Catalysts Zhu, Rongmei; Ding, Jiawei; Xu, Yuxia Small, Vol. 14, Issue 50 https://doi.org/10.1002/smll.201803576	journal	October 2018
Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels Wei, Chao; Feng, Zhenxing; Scherer, Günther G. Advanced Materials, Vol. 29, Issue 23 https://doi.org/10.1002/adma.201606800	journal	April 2017
Bifunctional application of sodium cobaltate as a catalyst and captor through CO oxidation and subsequent CO ₂ chemisorption processes Vera, Elizabeth; Alcántar-Vázquez, Brenda; Duan, Yuhua RSC Advances, Vol. 6, Issue 3 https://doi.org/10.1039/c5ra22749f	journal	January 2016
Transition metal oxide-based oxygen reduction reaction electrocatalysts for energy conversion systems with aqueous electrolytes Xue, Yejian; Sun, Shanshan; Wang, Qin Journal of Materials Chemistry A, Vol. 6, Issue 23 https://doi.org/10.1039/c7ta10569j	journal	January 2018
Electronic Structure Engineering of LiCoO ₂ toward Enhanced Oxygen Electrocatalysis Zheng, Xiaobo; Chen, Yaping; Zheng, Xusheng Advanced Energy Materials, Vol. 9, Issue 16 https://doi.org/10.1002/aenm.201803482	journal	February 2019

Similar Records

Electronic Structure of LiCoO₂ Surfaces and Effect of Al Substitution

Journal Article · Mon Mar 18 00:00:00 EDT 2019 · Journal of Physical Chemistry. C · OSTI ID:1265784

Hong, Liang; Hu, Linhua; Freeland, John W.; +3 more

Lattice model calculation of the strain energy density and other properties of crystalline LiCoO{sub 2}

Journal Article · Mon Jun 01 00:00:00 EDT 1998 · Journal of Applied Physics · OSTI ID:1265784

Hart, F X; Bates, J B

Preferred orientation of polycrystalline LiCoO{sub 2} films

Journal Article · Sat Jan 01 00:00:00 EST 2000 · Journal of the Electrochemical Society · OSTI ID:1265784

Bates, J B; Dudney, N J; Neudecker, B J; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
EELS
lithium intercalation
nanorods
oxygen evolution reaction
oxygen reduction reaction

Title: Role of LiCoO2 Surface Terminations in Oxygen Reduction and Evolution Kinetics

Citation Formats

References (25)

Cited By (14)

Similar Records

Related Subjects

Title: Role of LiCoO₂ Surface Terminations in Oxygen Reduction and Evolution Kinetics