The electrochemical behavior of polysulfides in tetrahydrofuran

Yamin, H.; Penciner, J.; Gorenshtain, A.; Elam, M.; Peled, E.

doi:10.1016/0378-7753(85)88022-8

Cited by 128 publications

(84 citation statements)

References 2 publications

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“…Because S 8 is the most stable oxidation product, it was concluded by the authors that S 8 and not a polysulfide was the most likely electrochemical product. 34,38 Due to similarities in the cyclic voltammetry features of Li-S batteries based on THF 19,34,37 and DOL-DME 17,35,39 solvents, it is likely that Li-S batteries based on these solvents share the same mechanism of oxidation.…”

Section: Resultsmentioning

confidence: 99%

Understanding the Charging Mechanism of Lithium-Sulfur Batteries Using Spatially Resolved Operando X-Ray Absorption Spectroscopy

Gorlin

Patel

Freiberg

et al. 2016

J. Electrochem. Soc.

119

134

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Replacement of conventional cars with battery electric vehicles (BEVs) offers an opportunity to significantly reduce future carbon dioxide emissions. One possible way to facilitate widespread acceptance of BEVs is to replace the lithium-ion batteries used in existing BEVs with a lithium-sulfur battery, which operates using a cheap and abundant raw material with a high specific energy density. These significant theoretical advantages of lithium-sulfur batteries over the lithium-ion technology have generated a lot of interest in the system, but the development of practical prototypes, which could be successfully incorporated into BEVs, remains slow. To accelerate the development of improved lithium-sulfur batteries, our work focuses on the mechanistic understanding of the processes occurring inside the battery. In particular, we study the mechanism of the charging process and obtain spatially resolved information about both solution and solid phase intermediates in two locations of an operating Li 2 S-Li battery: the cathode and the separator. These measurements were made possible through the combination of a spectro-electrochemical cell developed in our laboratory and synchrotron based operando X-ray absorption spectroscopy measurements. Using the generated data, we identify a charging mechanism in a standard DOL-DME based electrolyte, which is consistent with both the first and subsequent charging processes. Lithium-sulfur (Li-S) batteries are an emerging battery technology that has the potential to meet the energy density and cost requirements of electric vehicles. Recently, several studies have identified that the attainment of areal capacities as high as 4-8 mAh/cm 2 while minimizing the electrolyte content are the key factors in meeting these requirements.1-3 The only currently commercialized Li-S battery has a significantly lower areal capacity of 2.5 mAh/cm 2 and operates in the presence of excess electrolyte, 4 necessitating significant technological breakthroughs to facilitate the possible use of Li-S batteries in the transportation sector. One of the main barriers to achieving such breakthroughs is the lack of fundamental understanding of the mechanism behind the operation of Li-S batteries. 1,5,6 In particular, it is not yet clear how the mechanism of discharge differs from the charge mechanism, 5 and if these two processes might change upon an increase in active material loading or reduction in electrolyte volume. 1 Consequently, there is a pressing need for performing operando characterization of Li-S batteries under a variety of conditions to identify fundamental aspects of the charging and discharging processes.One attractive but insufficiently explored system for a mechanistic characterization of Li-S batteries is the charging process of a Li 2 S cathode, a possible alternative to the conventional S 8 cathode, with a potential to enable batteries with silicon or tin rather than lithium anodes. 7,8 Specifically, it has been recently reported that a Li-S battery, which is assembled in a discharged s...

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Section: Resultsmentioning

confidence: 99%

Understanding the Charging Mechanism of Lithium-Sulfur Batteries Using Spatially Resolved Operando X-Ray Absorption Spectroscopy

Gorlin

Patel

Freiberg

et al. 2016

J. Electrochem. Soc.

119

134

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“…It was also shown that the favored chain length of polysulfides is related to D, lower D values favor the formation of longer chains. Reduction of sulfur and polysulfides in DMF [16], THF [17] and at a glassy carbon electrode in THF [18,19] were also investigated. Ultraviolet (UV)-visible, electron spin resonance (ESR), Raman spectra, CV and time resolved spectro-electrochemical techniques were adopted for these studies.…”

Section: Early Studiesmentioning

confidence: 99%

Lithium/Sulfur Secondary Batteries: A Review

Zhao

Cheruvally

Kim

et al. 2016

Journal of Electrochemical Science and Technology

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Lithium batteries based on elemental sulfur as the cathode-active material capture great attraction due to the high theoretical capacity, easy availability, low cost and non-toxicity of sulfur. Although lithium/sulfur (Li/S) primary cells were known much earlier, the interest in developing Li/S secondary batteries that can deliver high energy and high power was actively pursued since early 1990's. A lot of technical challenges including the low conductivity of sulfur, dissolution of sulfurreduction products in the electrolyte leading to their migration away from the cathode, and deposition of solid reaction products on cathode matrix had to be tackled to realize a high and stable performance from rechargeable Li/S cells. This article presents briefly an overview of the studies pertaining to the different aspects of Li/S batteries including those that deal with the sulfur electrode, electrolytes, lithium anode and configuration of the batteries.

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Section: Introductionmentioning

confidence: 99%

“…Since both polysulfide species were soluble, both high rate discharge and recharge were expected [2] Li2S4 + 2Li ~ 2Li~S~ [2] In another, more recent approach, the alkali metal polysulfides were used in electrolytes in which the polysultides were insoluble. The resulting cells had a much longer storage life, but high current capabilities of the cells were limited (2). Both previous examples of polysulfide electrochemistry promised high gravimetric energy densities, but limitations on power capability and/or storage have, thus far, prevented commercial development of the systems.…”

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confidence: 99%

“…In one case, the lithium polysulfides were dissolved in a THF based organic electrolyte and discharged at a porous carbon electrode, giving a rechargeable cathode (1). Since both polysulfide species were soluble, both high rate discharge and recharge were expected [2] Li2S4 + 2Li ~ 2Li~S~[2]In another, more recent approach, the alkali metal polysulfides were used in electrolytes in which the polysultides were insoluble. The resulting cells had a much longer storage life, but high current capabilities of the cells were limited (2).…”

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confidence: 99%

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Transition Metal Polysulfides as Battery Cathodes

Bowden¹,

Barnette²,

Demuth³

1988

J. Electrochem. Soc.

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Amorphous polysulfides of iron, nickel, and cobalt were prepared and characterized. The resulting compounds, Co2S7, Co2S9, Ni2ST, and Fe3Ss were evaluated as cathode materials in organic electrolyte lithium batteries. The cobalt compounds in particular delivered very high capacities of 1-1.2 A-h/g at voltages around 1.SV. The resulting cells possessed high gravimetric and volumetric energy densities.Sulfur is a very high energy density cathode for a lithium battery. Since elemental sulfur is an extremely good insulator, it has poor properties as an electrode. Sulfur is also soluble in some organic solvents, and tends to form polysulfides which are even more soluble in the presence of an alkali metal sulfide. Thus, sulfur does not appear to be an attractive candidate material for use in an organic electrolyte ambient temperature lithium battery. Metal sulfides with a fully reduced sulfur, such as FeS, do not utilize the high energy density of sulfur, since the sulfur does not participate in the overall reaction [1] 2Li+ FeS -~ Li2S + Fe[1]Earlier workers have tried to utilize the high energy densities of sulfur by using alkali metal polysulfides. In one case, the lithium polysulfides were dissolved in a THF based organic electrolyte and discharged at a porous carbon electrode, giving a rechargeable cathode (1). Since both polysulfide species were soluble, both high rate discharge and recharge were expected [2] Li2S4 + 2Li ~ 2Li~S~[2]In another, more recent approach, the alkali metal polysulfides were used in electrolytes in which the polysultides were insoluble. The resulting cells had a much longer storage life, but high current capabilities of the cells were limited (2). Both previous examples of polysulfide electrochemistry promised high gravimetric energy densities, but limitations on power capability and/or storage have, thus far, prevented commercial development of the systems. A composite approach is to combine the very high energy density of sulfur with the insolubility and good electrochemical behavior of a transition metal sulfide. An excellent example of such a compound, which combines both sulfur capacity and sulfide cathode characteristics, is iron pyrite, FeS2. The electrochemistry of iron pyrite has been studied and very high gravimetric and volumetric energy densities have been shown to be attainable (3). The discharge of FeS2 is a complex process, unlike the simplified form [3] shown below, although this appears to approximate the final products and stoichiometryThere are numerous examples of transition metal disulfides to choose from, such as COS2, NiS2, and MnS2, as well as FeS2. Metal trisulfides and higher sulfides are much less well known, with TiS3 and VS4 being the only *Electrochemical Society Active Member.well-known first row polysulfides and MoS3 and NbS3 in the second transition series. This is in substantial contrast to the alkali metals, where species such as Cs2S~ and Na2S5 are comparatively stable and well known. In view of the growing chemistry of polysulfide complexes fr...

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The electrochemical behavior of polysulfides in tetrahydrofuran

Cited by 128 publications

References 2 publications

Understanding the Charging Mechanism of Lithium-Sulfur Batteries Using Spatially Resolved Operando X-Ray Absorption Spectroscopy

Understanding the Charging Mechanism of Lithium-Sulfur Batteries Using Spatially Resolved Operando X-Ray Absorption Spectroscopy

Lithium/Sulfur Secondary Batteries: A Review

Transition Metal Polysulfides as Battery Cathodes

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