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Title: Effect of the size-selective silver clusters on lithium peroxide morphology in lithium–oxygen batteries

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms5895· OSTI ID:1356644
 [1];  [2];  [2];  [2];  [1];  [3];  [3];  [2];  [2];  [1];  [1];  [4];  [4];  [5];  [1];  [6]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Electron Microscopy Center
  4. Hanyang Univ., Seoul (Korea, Republic of). Dept. of Energy Engineering
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division. Nanoscience and Technology Division; Yale Univ., New Haven, CT (United States). Dept. of Chemical and Environmental Engineering; Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division. Nanoscience and Technology Division

Lithium–oxygen batteries have the potential needed for long-range electric vehicles, but the charge and discharge chemistries are complex and not well understood. The active sites on cathode surfaces and their role in electrochemical reactions in aprotic lithium–oxygen cells are difficult to ascertain because the exact nature of the sites is unknown. In this paper, we report the deposition of subnanometre silver clusters of exact size and number of atoms on passivated carbon to study the discharge process in lithium–oxygen cells. The results reveal dramatically different morphologies of the electrochemically grown lithium peroxide dependent on the size of the clusters. This dependence is found to be due to the influence of the cluster size on the formation mechanism, which also affects the charge process. Finally, the results of this study suggest that precise control of subnanometre surface structure on cathodes can be used as a means to improve the performance of lithium–oxygen cells.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Hanyang Univ., Seoul (Korea, Republic of)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Knowledge Economy (Korea, Republic of); National Research Foundation of Korea (NRF)
Grant/Contract Number:
AC02-06CH11357; 20124010203310; 2009-0092780
OSTI ID:
1356644
Journal Information:
Nature Communications, Vol. 5; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 152 works
Citation information provided by
Web of Science

References (45)

Effects of Electrolyte Salts on the Performance of Li–O 2 Batteries journal February 2013
A Reversible and Higher-Rate Li-O2 Battery journal July 2012
Screening for Superoxide Reactivity in Li-O 2 Batteries: Effect on Li 2 O 2 /LiOH Crystallization journal February 2012
The Effect of Oxygen Crossover on the Anode of a Li-O 2 Battery using an Ether-Based Solvent: Insights from Experimental and Computational Studies journal December 2012
The Carbon Electrode in Nonaqueous Li–O2 Cells
  • Ottakam Thotiyl, Muhammed M.; Freunberger, Stefan A.; Peng, Zhangquan
  • Journal of the American Chemical Society, Vol. 135, Issue 1, p. 494-500 https://doi.org/10.1021/ja310258x
journal December 2012
Compatibility of lithium salts with solvent of the non-aqueous electrolyte in Li–O2 batteries journal January 2013
Size-Dependent Subnanometer Pd Cluster (Pd 4 , Pd 6 , and Pd 17 ) Water Oxidation Electrocatalysis journal June 2013
In situ fabrication of porous-carbon-supported α-MnO2 nanorods at room temperature: application for rechargeable Li–O2 batteries journal January 2013
Hierarchically Porous Graphene as a Lithium–Air Battery Electrode journal November 2011
Trends in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium journal March 2012
Reactions in the Rechargeable Lithium–O 2 Battery with Alkyl Carbonate Electrolytes journal May 2011
Synthesis, Characterization, and Structural Modeling of High-Capacity, Dual Functioning MnO 2 Electrode/Electrocatalysts for Li-O 2 Cells journal July 2012
The Role of Catalysts and Peroxide Oxidation in Lithium-Oxygen Batteries journal November 2012
Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li–O 2 Batteries journal March 2012
Aprotic and Aqueous Li–O2 Batteries journal April 2014
Platinum−Gold Nanoparticles: A Highly Active Bifunctional Electrocatalyst for Rechargeable Lithium−Air Batteries journal September 2010
Rate-Dependent Morphology of Li 2 O 2 Growth in Li–O 2 Batteries journal November 2013
Selective Propene Epoxidation on Immobilized Au 6-10 Clusters: The Effect of Hydrogen and Water on Activity and Selectivity journal February 2009
Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge journal January 2013
Evidence for lithium superoxide-like species in the discharge product of a Li–O2 battery journal January 2013
Strong Effects of Cluster Size and Air Exposure on Oxygen Reduction and Carbon Oxidation Electrocatalysis by Size-Selected Pt n ( n ≤ 11) on Glassy Carbon Electrodes journal February 2013
Mechanisms of Morphological Evolution of Li2O2 Particles during Electrochemical Growth journal March 2013
A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries journal August 2013
Theoretical evidence for low kinetic overpotentials in Li-O 2 electrochemistry journal January 2013
Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects journal April 2010
Rechargeable Li-Air Batteries with Carbonate-Based Liquid Electrolytes journal January 2010
Increased Stability Toward Oxygen Reduction Products for Lithium-Air Batteries with Oligoether-Functionalized Silane Electrolytes journal December 2011
Lithium Peroxide Surfaces Are Metallic, While Lithium Oxide Surfaces Are Not journal December 2011
Oxygen reduction reaction catalyst on lithium/air battery discharge performance journal January 2011
On the Efficacy of Electrocatalysis in Nonaqueous Li–O 2 Batteries journal November 2011
Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium–O2 batteries journal November 2012
Synthesis of Porous Carbon Supported Palladium Nanoparticle Catalysts by Atomic Layer Deposition: Application for Rechargeable Lithium–O2 Battery journal August 2013
A Polymer Electrolyte-Based Rechargeable Lithium/Oxygen Battery journal January 1996
Influence of Li2O2 morphology on oxygen reduction and evolution kinetics in Li–O2 batteries journal January 2013
Stability of Lithium Superoxide LiO2 in the Gas Phase: Computational Study of Dimerization and Disproportionation Reactions
  • Bryantsev, Vyacheslav S.; Blanco, Mario; Faglioni, Francesco
  • The Journal of Physical Chemistry A, Vol. 114, Issue 31, p. 8165-8169 https://doi.org/10.1021/jp1047584
journal August 2010
Carbon black cathodes for lithium oxygen batteries: Influence of porosity and heteroatom-doping journal November 2013
α-MnO2 Nanowires: A Catalyst for the O2 Electrode in Rechargeable Lithium Batteries journal June 2008
Electrical conductivity in Li 2 O 2 and its role in determining capacity limitations in non-aqueous Li-O 2 batteries journal December 2011
Interactions of Dimethoxy Ethane with Li 2 O 2 Clusters and Likely Decomposition Mechanisms for Li–O 2 Batteries journal April 2013
Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation journal September 2008
Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane journal February 2009
First-principles study of the oxygen evolution reaction of lithium peroxide in the lithium-air battery journal November 2011
Selective Propene Epoxidation on Immobilized Au 6–10 Clusters: The Effect of Hydrogen and Water on Activity and Selectivity journal January 2009
The Role of Catalysts and Peroxide Oxidation in Lithium-Oxygen Batteries journal December 2012
α-MnO2 Nanowires: A Catalyst for the O2 Electrode in Rechargeable Lithium Batteries journal June 2008

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A lithium–oxygen battery based on lithium superoxide journal January 2016
Urchin-like NiO–NiCo 2 O 4 heterostructure microsphere catalysts for enhanced rechargeable non-aqueous Li–O 2 batteries journal January 2019
State-of-the-art characterization techniques for advanced lithium-ion batteries journal March 2017
Catalysis by clusters with precise numbers of atoms journal July 2015
A High Voltage Organic Redox Flow Battery with Redox Couples O 2 /Tetrabutylammonium Complex and Tris(4-bromophenyl)amine as Redox Active Species journal January 2018
Enhancing oxygen adsorption capabilities in Li–O 2 battery cathodes through solid perfluorocarbons journal January 2017
A lithium ion/oxygen hybrid battery with high energy and high power journal January 2018
Highly Stable Oxygen Electrodes Enabled by Catalyst Redistribution through an In Situ Electrochemical Method journal February 2019
Platinum-Coated Hollow Graphene Nanocages as Cathode Used in Lithium-Oxygen Batteries journal August 2016
Raman Spectroscopy in Lithium-Oxygen Battery Systems journal August 2015
Electron microscopy and its role in advanced lithium-ion battery research journal January 2019
PdNi alloy decorated 3D hierarchically N, S co-doped macro–mesoporous carbon composites as efficient free-standing and binder-free catalysts for Li–O 2 batteries journal January 2018
Ruthenium oxide modified hierarchically porous boron-doped graphene aerogels as oxygen electrodes for lithium–oxygen batteries journal January 2018
Perspective: Size selected clusters for catalysis and electrochemistry journal March 2018
Hydrogen evolution reaction (HER) on Au@Ag ultrananoclusters as electro-catalysts journal January 2018
Effect of Componential Proportion in Bimetallic Electrocatalysts on the Aprotic Lithium-Oxygen Battery Performance journal April 2018
Biomass-derived hierarchically porous carbon skeletons with in situ decorated IrCo nanoparticles as high-performance cathode catalysts for Li–O 2 batteries journal January 2019
Insights into Structural Evolution of Lithium Peroxides with Reduced Charge Overpotential in Li−O 2 System journal June 2019
Recent advances in understanding of the mechanism and control of Li 2 O 2 formation in aprotic Li–O 2 batteries journal January 2017
Von isolierten Ionen zu mehrschichtigen funktionellen Materialien durch sanfte Landung von Ionen journal November 2018
Pd-Impregnated NiCo 2 O 4 nanosheets/porous carbon composites as a free-standing and binder-free catalyst for a high energy lithium–oxygen battery journal January 2017
Subnanometer cobalt oxide clusters as selective low temperature oxidative dehydrogenation catalysts journal February 2019
Functional and stability orientation synthesis of materials and structures in aprotic Li–O 2 batteries journal January 2018
Transient High-Power Output of Aprotic Li-O 2 Batteries Based on Cathode Capacitance Behavior journal January 2018
Realizing the Embedded Growth of Large Li 2 O 2 Aggregations by Matching Different Metal Oxides for High-Capacity and High-Rate Lithium Oxygen Batteries journal July 2017
Advances in Manganese-Based Oxides Cathodic Electrocatalysts for Li-Air Batteries journal February 2018
A 3D porous nitrogen-doped carbon-nanofiber-supported palladium composite as an efficient catalytic cathode for lithium–oxygen batteries journal January 2017
From Isolated Ions to Multilayer Functional Materials Using Ion Soft Landing journal November 2018
A free standing Ru–TiC nanowire array/carbon textile cathode with enhanced stability for Li–O 2 batteries journal January 2018
Graphene-Modified 3D Copper Foam Current Collector for Dendrite-Free Lithium Deposition journal November 2019