Characterization of Reactions and Products of the Discharge and Forced Overdischarge of Li /  SO 2 Cells

Rupich, M.W.; Pitts, L.; Abraham, K. M.

doi:10.1149/1.2124314

Cited by 60 publications

(60 citation statements)

References 8 publications

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“…This clearly demonstrates the thermal instability of LiFSi:AN based highlyconcentrated electrolytes in contact with partially lithiated graphite specially considering the fact that this thermal runaway happened under inert atmosphere. AN has been proposed to be reduced at the surface of Li metal electrodes following equation 2 [40]:…”

Section: 1mentioning

confidence: 99%

The use of deuterated ethyl acetate in highly concentrated electrolyte as a low-cost solvent for in situ neutron diffraction measurements of Li-ion battery electrodes

Petibon

Sharma

et al. 2015

Electrochimica Acta

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Section: 1mentioning

confidence: 99%

The use of deuterated ethyl acetate in highly concentrated electrolyte as a low-cost solvent for in situ neutron diffraction measurements of Li-ion battery electrodes

Petibon

Sharma

et al. 2015

Electrochimica Acta

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“…AN spontaneously reacts with lithium metal (i.e., a strong reducing agent), and thus, a lithium metal electrode does not work reversibly in AN electrolytes. 11 For the same reason, there is no report on reversible lithium intercalation into graphite in AN solutions, excluding AN from the candidate of electrolytes for lithium-ion batteries. Hence, overcoming the poor reductive stability of AN will bring about substantial progress in next-generation advanced batteries.…”

Section: ■ Introductionmentioning

confidence: 99%

Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion Batteries

et al. 2014

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The development of a stable, functional electrolyte is urgently required for fast-charging and high-voltage lithium-ion batteries as well as next-generation advanced batteries (e.g., Li−O 2 systems). Acetonitrile (AN) solutions are one of the most promising electrolytes with remarkably high chemical and oxidative stability as well as high ionic conductivity, but its low stability against reduction is a critical problem that hinders its extensive applications. Herein, we report enhanced reductive stability of a superconcentrated AN solution (>4 mol dm −3 ). Applying it to a battery electrolyte, we demonstrate, for the first time, reversible lithium intercalation into a graphite electrode in a reduction-vulnerable AN solvent. Moreover, the reaction kinetics is much faster than in a currently used commercial electrolyte. First-principle calculations combined with spectroscopic analyses reveal that the peculiar reductive stability arises from modified frontier orbital characters unique to such superconcentrated solutions, in which all solvents and anions coordinate to Li + cations to form a fluid polymeric network of anions and Li + cations. ■ INTRODUCTIONWith growing public concern about environmental and energy issues, considerable effort has been devoted to the development of cutting-edge electrochemical energy-storage technologies such as high-voltage and fast-charging lithium-ion batteries as well as next-generation lithium−oxygen batteries. 1−4 A key material in such advanced batteries is a stable, functional electrolyte that allows for reversible and rapid positive/negative electrode reactions without suffering from severe oxidative/ reductive decompositions. In particular, an oxidation-tolerant electrolyte is primarily required to meet the recent remarkable progress and diversification of positive-electrode materials for high-voltage advanced batteries.Acetonitrile (AN) is one of the most oxidation-tolerant organic solvents. In addition, due to its high dielectric constant, 5 AN can easily dissolve electrolyte salts to exhibit considerably high ionic conductivity. Because of these attractive features, AN solutions are a promising electrolyte for various electrochemical devices. 6−9 Particularly, applying them to lithium-ion batteries will eliminate the conventional voltage limitation (∼4.2 V) based on the electrochemical window of currently used carbonate-based electrolytes to open the possibility of high-voltage operation with a 5 V-class positive electrode. 4,10 Furthermore, the excellent ionic transport property will possibly realize fast-charging lithium-ion batteries, which are urgently required for automobile applications.Despite these remarkable advantages, AN has not found extensive application in batteries. This is primarily due to its crucially poor reductive stability. AN spontaneously reacts with lithium metal (i.e., a strong reducing agent), and thus, a lithium metal electrode does not work reversibly in AN electrolytes. 11 For the same reason, there is no report on reversible lithium intercalati...

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“…The ex situ X-ray diffraction spectra in Fig. 2d reveal that characteristic peaks of Li 2 S 2 O 4 appear and grow during discharge without any notable by-products, followed by the reduction of these peaks during the charge and their complete disappearance after the end of the charge3148. These results evidently confirm that the reversible formation and decomposition of Li 2 S 2 O 4 is the major electrochemical reaction occurring in the Li-SO 2 system using an EC/DMC electrolyte, which is consistent with the DFT calculations.…”

Section: Resultsmentioning

confidence: 97%

High-efficiency and high-power rechargeable lithium–sulfur dioxide batteries exploiting conventional carbonate-based electrolytes

Park

Lim

et al. 2017

Nat Commun

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Shedding new light on conventional batteries sometimes inspires a chemistry adoptable for rechargeable batteries. Recently, the primary lithium-sulfur dioxide battery, which offers a high energy density and long shelf-life, is successfully renewed as a promising rechargeable system exhibiting small polarization and good reversibility. Here, we demonstrate for the first time that reversible operation of the lithium-sulfur dioxide battery is also possible by exploiting conventional carbonate-based electrolytes. Theoretical and experimental studies reveal that the sulfur dioxide electrochemistry is highly stable in carbonate-based electrolytes, enabling the reversible formation of lithium dithionite. The use of the carbonate-based electrolyte leads to a remarkable enhancement of power and reversibility; furthermore, the optimized lithium-sulfur dioxide battery with catalysts achieves outstanding cycle stability for over 450 cycles with 0.2 V polarization. This study highlights the potential promise of lithium-sulfur dioxide chemistry along with the viability of conventional carbonate-based electrolytes in metal-gas rechargeable systems.

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Characterization of Reactions and Products of the Discharge and Forced Overdischarge of Li / SO 2 Cells

Cited by 60 publications

References 8 publications

The use of deuterated ethyl acetate in highly concentrated electrolyte as a low-cost solvent for in situ neutron diffraction measurements of Li-ion battery electrodes

The use of deuterated ethyl acetate in highly concentrated electrolyte as a low-cost solvent for in situ neutron diffraction measurements of Li-ion battery electrodes

Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion Batteries

High-efficiency and high-power rechargeable lithium–sulfur dioxide batteries exploiting conventional carbonate-based electrolytes

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