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Title: Hybrid Li-Ion and Li-O2 Battery Enabled by Oxyhalogen-Sulfur Electrochemistry

Journal Article · · Joule

We report that the large voltage hysteresis between charge and discharge results in significant energy loss, which hinders practical application of the high-energy Li-O2 battery. Oxyhalogen-sulfur electrochemistry offers a new hybrid Li-ion/Li-O2 battery, where both Li ions and O anions are reversibly stored in the MoS2 structure. A Li2MoO2S2 compound is formed as the main discharge product that has never been previously observed in the literature. The reaction mechanism and the structure of the Li2MoO2S2 are probed by Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, differential electrochemical mass spectrometry, and UV-visible spectroscopy. The results show that the MoS2 is oxidized during discharge and is recovered during charge. The iodine intermediates play an important role in triggering the sequence of electrochemical and chemical reactions in the cell. Finally, the Li2MoO2S2 is isostructural to the Li2MoO4 rather than adopting structures of other known molybdenum oxysulfides.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Science Foundation (NSF); USDOE
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231
OSTI ID:
1575086
Alternate ID(s):
OSTI ID: 1493717
Journal Information:
Joule, Vol. 2, Issue 11; ISSN 2542-4351
Publisher:
Elsevier - Cell PressCopyright Statement
Country of Publication:
United States
Language:
English

References (51)

Electric Field Effect in Atomically Thin Carbon Films journal October 2004
Phase Diagrams for Systems with Low Free Energy Variation:  A Coupled Theory/Experiments Method Applied to Li-Graphite journal March 2008
Electrochemical investigation of the P2–NaxCoO2 phase diagram journal December 2010
Phase Diagram of Olivine Na x FePO 4 (0 < x < 1) journal October 2013
A review of cathode materials and structures for rechargeable lithium–air batteries journal January 2015
Critical Challenges in Rechargeable Aprotic Li-O 2 Batteries journal February 2016
Advances in understanding mechanisms underpinning lithium–air batteries journal September 2016
The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li–O2 batteries journal November 2014
Promoting solution phase discharge in Li–O2 batteries containing weakly solvating electrolyte solutions journal April 2016
A lithium–oxygen battery based on lithium superoxide journal January 2016
Cycling Li-O2 batteries via LiOH formation and decomposition journal October 2015
Implications of 4 e Oxygen Reduction via Iodide Redox Mediation in Li–O 2 Batteries journal September 2016
Comment on "Cycling Li-O2 batteries via LiOH formation and decomposition" journal May 2016
Comment on "Cycling Li-O2 batteries via LiOH formation and decomposition" journal May 2016
Coordination chemistry of Mo- and W-S compounds and some aspects of hydrodesulfurization catalysis journal January 1986
DFT Calculations of Unpromoted and Promoted MoS2-Based Hydrodesulfurization Catalysts journal October 1999
Single-layer MoS2 as an efficient photocatalyst journal January 2013
Photocatalytic Stability of Single- and Few-Layer MoS 2 journal October 2015
Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction journal November 2013
Hierarchical MoS 2 microboxes constructed by nanosheets with enhanced electrochemical properties for lithium storage and water splitting journal January 2014
Kinetic Study of Hydrogen Evolution Reaction over Strained MoS 2 with Sulfur Vacancies Using Scanning Electrochemical Microscopy journal April 2016
Intercalation chemistry of molybdenum disulfide journal January 2002
Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts journal July 2007
Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis journal October 2012
Infrared and Raman Studies of Long-Wavelength Optical Phonons in Hexagonal Mo S 2 journal June 1971
Operando Observation of the Gold–Electrolyte Interface in Li–O 2 Batteries journal October 2014
Raman Spectroscopy in Lithium-Oxygen Battery Systems journal August 2015
Properties of Li2MoO4 single crystals grown by Czochralski technique journal September 2014
Molecular Spectroscopy by Means of ESCA II. Sulfur compounds. Correlation of electron binding energy with structure journal May 1970
Oxyhalogen–sulfur chemistry Oxidation of 2-aminoethanethiolsulfuric acid by iodate in acidic medium journal January 1997
Oxyhalogen–sulfur chemistry — Kinetics and mechanism of oxidation of methionine by aqueous iodine and acidified iodate journal June 2009
Unraveling the Complex Role of Iodide Additives in Li–O 2 Batteries journal July 2017
Raman Studies of Iodic Acid and Sodium Iodate journal November 1965
Electronic Spectrum of IO− in Solution journal July 1965
Iodine chemistry in the +1 oxidation state. I. The electronic spectra of OI , HOI, and H 2 OI + journal September 1985
Iodine chemistry in the +1 oxidation state. II. A Raman and uv–visible spectroscopic study of the disproportionation of hypoiodite in basic solutions journal December 1986
A novel aqueous lithium–oxygen cell based on the oxygen-peroxide redox couple journal January 2015
Response to Comment on "Cycling Li-O2 batteries via LiOH formation and decomposition" journal May 2016
Reactions of iodine intermediates in iodate-hydrogen peroxide oscillators journal April 1987
Reactions involving hydrogen peroxide, iodine, and iodate ion. V. Introduction to the oscillatory decomposition of hydrogen peroxide journal November 1974
Electrolyte Composition in Li/O 2 Batteries with LiI Redox Mediators: Solvation Effects on Redox Potentials and Implications for Redox Shuttling journal January 2018
Molybdenum(VI) speciation in sulfidic waters: journal April 2000
Kinetics of the interconversion of sulfido- and oxomolybdate(VI) species MoOxS4-x2- in aqueous solutions journal October 1980
Thermal decomposition of (NH4)2MoO2S2, (NH4)2MoS4, (NH4)2WO2S2 and (NH4)2WS4 journal June 1973
Activated Lithium-Metal-Oxides as Catalytic Electrodes for Li–O2 Cells journal January 2011
Vision for Designing High-Energy, Hybrid Li Ion/Li–O 2 Cells journal October 2013
Design Strategies, Practical Considerations, and New Solution Processes of Sulfide Solid Electrolytes for All-Solid-State Batteries journal April 2018
Lithium/Molybdenum Oxysulfide Secondary Batteries journal February 1989
Enhanced Power and Rechargeability of a Li−O 2 Battery Based on a Hierarchical-Fibril CNT Electrode journal December 2012
�bergangsmetallchalkogenverbindungen. �ber Dithiomolybdate und -wolframate (NH4)2MoO2S2 und (NH4)2WO2S2, Verbindungen mit starken Wasserstoffbr�cken journal July 1970
Trade-Offs in Capacity and Rechargeability in Nonaqueous Li–O 2 Batteries: Solution-Driven Growth versus Nucleophilic Stability journal March 2015

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