High Performance C/S Composite Cathodes with Conventional Carbonate-Based Electrolytes in Li-S Battery

Zheng, Shiyou; Han, Pan; Han, Zhuo; Zhang, Huijuan; Tang, Zhihong; Yang, Jing

doi:10.1038/srep04842

Cited by 104 publications

(78 citation statements)

References 42 publications

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“…The corresponding cells can exhibit excellent rate capability and cycling stability. Similar results with S/porous carbon composite as cathodes in carbonate electrolyte were also obtained by some other groups with good electrochemical performances (Wang et al, 2002Zheng et al, 2014). However, one of the obvious problems of this strategy is the low sulfur loading due to the small pore volume contributed by micropores.…”

Section: Carbonate-based Electrolytessupporting

confidence: 70%

Developments of Electrolyte Systems for Lithiumâ€“Sulfur Batteries: A Review

Zhang³

et al. 2015

Front. Energy Res.

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With a theoretical specific energy five times higher than that of lithium-ion batteries (2,600 vs.~500Wh kg −1 ), lithium-sulfur (Li-S) batteries have been considered as one of the most promising energy storage systems for the electrification of vehicles. However, both the polysulfide shuttle effects of the sulfur cathode and dendrite formation of the lithium anode are still key limitations to practical use of traditional Li-S batteries. In this review, we focus on the recent developments in electrolyte systems. First, we start with a brief discussion on fundamentals of Li-S batteries and key challenges associated with traditional liquid cells. We then introduce the most recent progresses in liquid systems, including ether-based, carbonate-based, and ionic liquid-based electrolytes. And then we move on to the advances in solid systems, including polymer and non-polymer electrolytes. Finally, the opportunities and perspectives for future research in both the liquid and solid Li-S batteries are presented.

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Section: Carbonate-based Electrolytessupporting

confidence: 70%

Developments of Electrolyte Systems for Lithiumâ€“Sulfur Batteries: A Review

Zhang³

et al. 2015

Front. Energy Res.

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“…Mechanism in the carbonate solvent based electrolytes.-Ultramicroporous carbons with a pore diameter smaller than 0.7 nm gained considerable interest as host matrix for sulfur in Li-S batteries since such sulfur confinement shows excellent electrochemical stability even in the carbonate based solvents. [39][40][41] It is well accepted that soluble polysulfides react with the carbonate based electrolytes via a nucleophilic addition or substitution reactions 42 leading to extensive degradation of electrolyte. In this work ultramicroporous carbon derived from coconut shell containing predominately micropores with a diameter of 0.5 nm has been used as host matrix for sulfur.…”

Section: Resultsmentioning

confidence: 99%

Polysulfides Formation in Different Electrolytes from the Perspective of X-ray Absorption Spectroscopy

Dominko

Vižintin

Aquilanti

et al. 2017

J. Electrochem. Soc.

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Li-S batteries are promising energy storage technology for the future, however there two major problems remained which need to be solved before successful commercialization. Capacity fading due to polysulfide shuttle and corrosion of lithium metal are directly connected with the type and quantity of electrolyte used in the cells. Several recent works show dependence of the electrochemical behavior of Li-S batteries on type of the electrolyte. In this work we compare and discuss a discharge mechanism of sulfur conversion in three different electrolytes based on measurements with sulfur K-edge XAS. The sulfur conversion mechanism in the ether based electrolytes, the most studied type of solvents in the Li-S batteries, which are enabling high solubility of polysulfides are compared with the fluorinated ether based electrolytes with a reduced polysulfide solubility and in carbonate based electrolytes with the sulfur confined into a ultramicroporous carbon. In all three cases the sulfur reduction proceeds through polysulfide intermediate phases with a difference on the type polysulfides detected at different steps of discharge. Electrification of road transport has increased the pressure on materials' scientists to improve performance of the current Li-ion batteries and to develop new advanced high energy battery technologies. 1Among several post lithium-ion technologies, the lithium sulfur (Li-S) batteries are recognized as the most promising for commercialization in the near future. A combination of lithium and sulfur in the electrochemical cell corresponds to the theoretical energy density of 2600 Wh/kg, while the maximum practically accessible energy density is predicted to be close to 600 Wh/kg.2,3 This is much higher compared to Li-ion batteries and besides that, sulfur is inexpensive and naturally abundant. Nevertheless, problems related to the solubility of polysulfides in the electrolyte and the related redox shuttle phenomena cause short cycle life, potential safety problems, poor cycling efficiency, and relative fast self-discharge. Additional problems of Li-S batteries are very low electronic conductivity of the both end members in the discharge and charge process (i.e. sulfur and Li 2 S) and extensive corrosion of the metal lithium anode.Different directions how to improve Li-S battery cycle life have been explored, like synthesis of the optimized porous host matrices with active sites for polysulfide anchoring, 4,5 design and optimization of separators which can effectively suppress polysulfide cross communication between electrodes 6,7 and protection of lithium by artificial SEI 8 or by additives. 9 While most of the research was performed in the binary mixture of solvents using alkyl ethers (glymes) and heterocyclic acetyl (dioxolane), less attention has been paid to the development of new electrolytes for Li-S batteries. 10 Reasons for that are nested in the requirements which should be fulfilled in the development of new formulations. First of all, electrolytes used in the electrochemical cells must...

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“…This type of behavior schematically presented in Fig. 1b is generally observed for organic carbonatebased electrolyte solutions, [13][14][15][16][17][18][19][20][21][22]24,25,27,31,33,35,36,39,40 as well as for bis(fluorosulfonyl)imide (FSI) anion-based ionic liquid electrolyte solutions. 28,37,38 For this type of the operation of Li-S cells voltage profiles differ from those commonly measured for conventioanal Li-S composite electrodes and are characterized by a single galvanostatic charge/discharge voltage plateau observed around 2.0 V vs. Li/Li + .…”

mentioning

confidence: 99%

“…It is remarkable that the voltage profiles measured with these types of cells with liquid electrolyte solutions are very similar to that of solid state Li-S cells 26,41 and for sulfurized carbon electrodes with sulfur covalently bound onto the surface of carbon particles. 18,[42][43][44] In the case of liquid electrolytes Wang et al proposed that this type of unique behavior (namely, the single plateau observation) relates to the reaction of Li ions after desolvation with sulfur encapsulated in the micropores under solvent deficient conditions and called this mechanism "quasi-solid-state reaction". 15,45 In most cases this mechanism is observed for composite S/C electrodes with very narrow micropores which width is lower than 1 nm, [14][15][16]19,20,22,23,28,40 but in some cases this type of operation was described also for larger pore size.…”

mentioning

confidence: 99%

Review—On the Mechanism of Quasi-Solid-State Lithiation of Sulfur Encapsulated in Microporous Carbons: Is the Existence of Small Sulfur Molecules Necessary?

Markevich

Salitra

Talyosef

et al. 2016

J. Electrochem. Soc.

102

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In this work we analyzed the phenomenon of quasi solid state (QSS) lithiation of sulfur-carbon (S/C) composite electrodes with sulfur confined in the micropores of carbon matrices based on our recent studies and data published in literature. We demonstrated that the existence of sulfur in the form of small molecules is not a necessary condition for the realization of QSS mechanism. QSS operation behavior was demonstrated both for carbons with small up to 1nm micropores and for carbons with larger pore size up to 2-3 nm. A key role in the operation of S/C electrodes via a QSS mechanism plays surface electrolyte interphase (SEI) which is formed on the surface of S/C composite during the initial discharge. The formation of SEI was supported by X-ray photoelectron spectroscopy and by scanning electron microscopy. Small pore size (up to 1 nm) of the carbon matrices has a positive effect on the cycling of S/C electrodes. A superior cycling performance for more than 3500 charge-discharge cycles was demonstrated for S/C composite electrodes based on carbons synthesized by carbonization of polyvinylidene dichloride (PVDC) resin. In recent years lithium-sulfur batteries have been the subject of very intensive research due to the high theoretical specific capacity of sulfur cathodes (1672 mA h g −1 ) which is an order of magnitude higher than that of lithiated transition-metal oxides and phosphates cathode materials used in commercial Li-ion batteries (140-200 mA h g −1 ). [1][2][3][4][5][6] This high capacity relates to the ability of sulfur atoms to accept two electrons resulting in the conversion of elemental sulfur to lithium sulfide (Li 2 S). Furthermore, sulfur is naturally abundant, environmentally friendly and relatively cheap.Due to the low electrical conductivity of elementary sulfur the addition of conductive additives or the use of conductive host materials it is necessary to ensure good performance of sulfur electrodes. Besides, during the discharge process elemental sulfur S 8 accepts electrons to give a chain of electroactive Li-polysulfides (Fig. 1a). The long-chain polysulfides Li 2 S n (4 ≤ n ≤ 8) are soluble in commonly used ethereal solvents and diffuse freely throughout the cell to the anode side where they are chemically reduced. This phenomenon known as the shuttle effect presents one of the main problems of Li-S cells. 7 The shuttle reactions prevent the possibility of extracting the full capacity of sulfur cathodes and lead to low Coulombic efficiency. Encapsulation of sulfur within activated carbons with high pores volume is one of the most effective approaches to mitigate the detrimental shuttle mechanism and stabilize composite sulfur cathodes during prolong cycling. 8-10The typical cyclic voltammetry and galvanostatic charge-discharge curves of the Li-S cell with C/S encapsulated cathode are shown in Fig. 1a. Two peaks observed in the cathodic voltammetric response of sulfur electrodes correspond to two plateaus observed in the voltage profiles of the discharge processes of these cathodes upon ...

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High Performance C/S Composite Cathodes with Conventional Carbonate-Based Electrolytes in Li-S Battery

Cited by 104 publications

References 42 publications

Developments of Electrolyte Systems for Lithiumâ€“Sulfur Batteries: A Review

Developments of Electrolyte Systems for Lithiumâ€“Sulfur Batteries: A Review

Polysulfides Formation in Different Electrolytes from the Perspective of X-ray Absorption Spectroscopy

Review—On the Mechanism of Quasi-Solid-State Lithiation of Sulfur Encapsulated in Microporous Carbons: Is the Existence of Small Sulfur Molecules Necessary?

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