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Title: A lithium–oxygen battery based on lithium superoxide

Journal Article · · Nature (London)
DOI:https://doi.org/10.1038/nature16484· OSTI ID:1352638
 [1];  [2];  [3];  [4];  [5];  [4];  [4];  [6];  [1];  [1];  [6];  [2];  [2];  [7];  [8];  [5];  [2];  [4];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Hanyang Univ., Seoul (Korea, Republic of). Dept. of Energy Engineering
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Univ. of Utah, Salt Lake City, UT (United States). Dept. of Metallurgical Engineering
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  5. Univ. of Illinois, Chicago, IL (United States). Dept. of Mechanical and Industrial Engineering
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  7. Univ. of Utah, Salt Lake City, UT (United States). Dept. of Metallurgical Engineering
  8. Univ. of Louisville, KY (United States). Conn Center for Renewable Energy Research

Batteries based on sodium superoxide and on potassium superoxide have recently been reported(1-3). But, there have been no reports of a battery based on lithium superoxide (LiO2), despite much research(4-8) into the lithium-oxygen (Li-O2) battery because of its potential high energy density. Several studies(9-16) of Li-O2 batteries have found evidence of LiO2 being formed as one component of the discharge product along with lithium peroxide (Li2O2). In addition, theoretical calculations have indicated that some forms of LiO2 may have a long lifetime(17). Our studies also suggest that it might be possible to form LiO2 alone for use in a battery. However, solid LiO2 has been difficult to synthesize in pure form(18) because it is thermodynamically unstable with respect to disproportionation, giving Li2O2 (refs 19, 20). We show that crystalline LiO2 can be stabilized in a Li-O2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li2O2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO2. Our results demonstrate that the LiO2 formed in the Li-O2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We also anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO2, which could open the way to high-energy-density batteries based on LiO2 as well as to other possible uses of this compound, such as oxygen storage.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
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)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1352638
Journal Information:
Nature (London), Vol. 529, Issue 7586; ISSN 0028-0836
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 562 works
Citation information provided by
Web of Science

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  • 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
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Platinum-Coated Hollow Graphene Nanocages as Cathode Used in Lithium-Oxygen Batteries journal August 2016
Au-Decorated Cracked Carbon Tube Arrays as Binder-Free Catalytic Cathode Enabling Guided Li 2 O 2 Inner Growth for High-Performance Li-O 2 Batteries journal September 2016
Biomass Organs Control the Porosity of Their Pyrolyzed Carbon journal December 2016
Mo 2 C/CNT: An Efficient Catalyst for Rechargeable Li-CO 2 Batteries journal May 2017
Holey 2D Nanosheets of Low-Valent Manganese Oxides with an Excellent Oxygen Catalytic Activity and a High Functionality as a Catalyst for Li-O 2 Batteries journal February 2018
3D-Printed MOF-Derived Hierarchically Porous Frameworks for Practical High-Energy Density Li-O 2 Batteries journal November 2018
Visualizing the Oxidation Mechanism and Morphological Evolution of the Cubic‐Shaped Superoxide Discharge Product in Na–Air Batteries journal February 2019
Constructing a High‐Strength Solid Electrolyte Layer by In Vivo Alloying with Aluminum for an Ultrahigh‐Rate Lithium Metal Anode journal December 2019
Cathode Surface-Induced, Solvation-Mediated, Micrometer-Sized Li 2 O 2 Cycling for Li-O 2 Batteries journal September 2016
In Situ Construction of Stable Tissue-Directed/Reinforced Bifunctional Separator/Protection Film on Lithium Anode for Lithium-Oxygen Batteries journal April 2017
A Water-/Fireproof Flexible Lithium-Oxygen Battery Achieved by Synergy of Novel Architecture and Multifunctional Separator journal November 2017
Bending-Tolerant Anodes for Lithium-Metal Batteries journal November 2017
Redox Mediators for Li-O 2 Batteries: Status and Perspectives journal November 2017
Calcium-Ion Batteries: Current State-of-the-Art and Future Perspectives journal July 2018
Fundamental Understanding of Water‐Induced Mechanisms in Li–O 2 Batteries: Recent Developments and Perspectives journal November 2018
Morphosynthesis of 3D Macroporous Garnet Frameworks and Perfusion of Polymer‐Stabilized Lithium Salts for Flexible Solid‐State Hybrid Electrolytes journal April 2019
Graphene-Based Nanocomposites for Energy Storage journal June 2016
Full Performance Nanoporous Graphene Based Li-O 2 Batteries through Solution Phase Oxygen Reduction and Redox-Additive Mediated Li 2 O 2 Oxidation journal December 2016
Optimized Bicompartment Two Solution Cells for Effective and Stable Operation of Li-O 2 Batteries journal August 2017
Enhanced Cyclability of Lithium-Oxygen Batteries with Electrodes Protected by Surface Films Induced via In Situ Electrochemical Process journal January 2018
Fundamental Understanding and Material Challenges in Rechargeable Nonaqueous Li-O 2 Batteries: Recent Progress and Perspective journal May 2018
Nature-Inspired Tri-Pathway Design Enabling High-Performance Flexible Li-O 2 Batteries journal January 2019
Highly Stable Oxygen Electrodes Enabled by Catalyst Redistribution through an In Situ Electrochemical Method journal February 2019
Commercialization of Lithium Battery Technologies for Electric Vehicles journal June 2019
Strategies Toward Stable Nonaqueous Alkali Metal–O 2 Batteries journal May 2019
Regulating the Catalytic Dynamics Through a Crystal Structure Modulation of Bimetallic Catalyst journal January 2020
Understanding LiOH Chemistry in a Ruthenium-Catalyzed Li-O 2 Battery journal November 2017
The Long-Term Stability of KO 2 in K-O 2 Batteries journal January 2018
Phenol-Catalyzed Discharge in the Aprotic Lithium-Oxygen Battery journal May 2017
Free-Standing Air Cathodes Based on 3D Hierarchically Porous Carbon Membranes: Kinetic Overpotential of Continuous Macropores in Li-O 2 Batteries journal May 2018
High‐Performance K–CO 2 Batteries Based on Metal‐Free Carbon Electrocatalysts journal February 2020
Carbon‐Free Cathode Materials for Li−O 2 Batteries journal February 2019
Understanding Rechargeable Li−O 2 Batteries via First‐Principles Computations journal March 2019
Safe Lithium‐Metal Anodes for Li−O 2 Batteries: From Fundamental Chemistry to Advanced Characterization and Effective Protection journal May 2019
FeOOH Nanocubes Anchored on Carbon Ribbons for Use in Li/O 2 Batteries journal February 2019
Graphene Oxide Sieving Membrane for Improved Cycle Life in High-Efficiency Redox-Mediated Li-O 2 batteries journal July 2018
Flexible, Flame-Resistant, and Dendrite-Impermeable Gel-Polymer Electrolyte for Li-O 2 /Air Batteries Workable Under Hurdle Conditions journal July 2018
Defect Chemistry in Discharge Products of Li-O 2 Batteries journal November 2018
Aprotic metal-oxygen batteries: recent findings and insights journal April 2017
Advances in understanding mechanisms underpinning lithium–air batteries journal September 2016
State-of-the-art characterization techniques for advanced lithium-ion batteries journal March 2017
A rechargeable lithium–oxygen battery with dual mediators stabilizing the carbon cathode journal July 2017
The role of nanotechnology in the development of battery materials for electric vehicles journal December 2016
Highly reversible zinc metal anode for aqueous batteries journal April 2018
A high-energy-density and long-life lithium-ion battery via reversible oxide–peroxide conversion journal October 2019
Theoretical prediction of LiScO 2 nanosheets as a cathode material for Li–O 2 batteries journal January 2018
C x N y particles@N-doped porous graphene: a novel cathode catalyst with a remarkable cyclability for Li–O 2 batteries journal January 2018
Nature inspired cathodes using high-density carbon papers with an eddy current effect for high-rate performance lithium–air batteries journal January 2018
Enhanced cycling stability of Li–O 2 batteries by using a polyurethane/SiO 2 /glass fiber nanocomposite separator journal January 2018
Promoting defective-Li 2 O 2 formation via Na doping for Li–O 2 batteries with low charge overpotentials journal January 2019
Exploring the charge reactions in a Li–O 2 system with lithium oxide cathodes and nonaqueous electrolytes journal January 2019
Lithium-air batteries: Challenges coexist with opportunities journal April 2019
High-capacity rechargeable batteries based on deeply cyclable lithium metal anodes journal May 2018
Tuning anion solvation energetics enhances potassium–oxygen battery performance journal July 2019
Nanostructured transition metal dichalcogenide electrocatalysts for CO 2 reduction in ionic liquid journal July 2016
A high-energy-density lithium-oxygen battery based on a reversible four-electron conversion to lithium oxide journal August 2018
Building Better Batteries in the Solid State: A Review journal November 2019
A Hybrid Na//K + -Containing Electrolyte//O 2 Battery with High Rechargeability and Cycle Stability journal January 2019
High-Energy-Density Metal-Oxygen Batteries: Lithium-Oxygen Batteries vs Sodium-Oxygen Batteries journal September 2017
Developing a “Water-Defendable” and “Dendrite-Free” Lithium-Metal Anode Using a Simple and Promising GeCl 4 Pretreatment Method journal July 2018
Review of Electrolytes in Nonaqueous Lithium-Oxygen Batteries journal March 2018
Recent Advances in Perovskite Oxides as Electrode Materials for Nonaqueous Lithium-Oxygen Batteries journal February 2017
Porous Carbon Composites for Next Generation Rechargeable Lithium Batteries journal May 2017
Hierarchically Porous, Ultrathick, “Breathable” Wood-Derived Cathode for Lithium-Oxygen Batteries journal September 2017
Effect of Componential Proportion in Bimetallic Electrocatalysts on the Aprotic Lithium-Oxygen Battery Performance journal April 2018
Insights into Structural Evolution of Lithium Peroxides with Reduced Charge Overpotential in Li−O 2 System journal June 2019
Hydronium-Ion Batteries with Perylenetetracarboxylic Dianhydride Crystals as an Electrode journal February 2017
Free-Standing Air Cathodes Based on 3D Hierarchically Porous Carbon Membranes: Kinetic Overpotential of Continuous Macropores in Li-O 2 Batteries journal May 2018
Why Do Lithium-Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect journal July 2016
Understanding LiOH Chemistry in a Ruthenium-Catalyzed Li-O 2 Battery journal November 2017
Three-Dimensional Flower-Like MoS 2 @Carbon Nanotube Composites with Interconnected Porous Networks and High Catalytic Activity as Cathode for Lithium-Oxygen Batteries journal July 2018
Alkali-Oxygen Batteries Based on Reversible Superoxide Chemistry journal October 2018
Applications of Conventional Vibrational Spectroscopic Methods for Batteries Beyond Li-Ion journal March 2018
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