A Li+-conductive microporous carbon–sulfur composite for Li-S batteries

Zhang, Wenhua; Qiao, Dan Yang; Pan, Jiaxin; Cao, Yuliang; Yang, Hanxi; Ai, Xinping

doi:10.1016/j.electacta.2012.09.086

Cited by 102 publications

(85 citation statements)

References 23 publications

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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 + .…”

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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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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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“…The charge and discharge curves of AZC-800/1KOH@S55 show a single plateau at every cycle, which is typical microporous characteristics. 13,19,20 The present reactions would be similar to solid-phase reactions of Li + in S, because any solvents cannot diffuse into the small micropores and no S reacts directly with Li + in an electrolyte phase. On the other hand, the charge-discharge curves of AZC-800/ 2KOH@S62 show distinctive characteristics; the discharge curves have a single plateau but the charge curves consist of two plateaus (Fig.…”

Section: Resultsmentioning

confidence: 99%

Preparation of Micropore-rich High Surface Area Activated Carbon from N-doped Carbon Precursor and its Application to Positive Electrode in Lithium-sulfur Battery

et al. 2017

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Micropore-rich activated carbon with high surface area and pore volume was prepared by alkali activation of azulmic carbon (AZC) precursor as nitrogen-doped carbon; AZC was a carbonized product from azulmic acid. We successfully loaded a large amount of sulfur (S) into micropores of the activated AZC. Our two kinds of activated AZC (BET surface area: 1,747 and 2,319 m 2 g −1) can include S up to 55 and 62 wt%, respectively. The former activated AZC including S can be charged and discharged with lithium (Li) ion transfer stably and reversibly in glyme-based and carbonate-based electrolytes. The latter activated AZC can be charged and discharged in a glyme-based electrolyte. These different characteristics are due to a difference in fine pore structure between them. Our microporous activated AZC with high S loading is promising material as positive S electrode for rechargeable Li-S batteries.

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“…For the first time, they introduced different allotropes of sulfur molecules (small sulfur molecules and cyclo-S 8 ) into microporous and mesoporous structures. The [124,[134][135][136][137][138][139]. Microporous structure plays an important role in the formation of small sulfur molecules.…”

Section: A Confined Sulfur Molecules In Microporous Structuresmentioning

confidence: 99%

“…Qian's group developed sulfur-rich S 1−x Se x /C composites [144]. The introduction of Se in the sulfur cathode has two important functions: (1) reducing the formation of long-chain polysulfides; and (2) Based on recent literature, the developed small sulfur molecule-based cathodes have some common characteristics: (1) sulfur should be confined in microporous structures; (2) low sulfur content C-S composites (mostly less than 50 wt%); (3) solid-phase Li-S reactions; and (4) highly stable and reversible electrochemical performance [124,135,143,146,147]. It should be noted that sulfur cathode with the low content and areal loading is hard to meet the requirement for high-energy Li-S batteries.…”

Section: A Confined Sulfur Molecules In Microporous Structuresmentioning

confidence: 99%

Structural Design of Lithium–Sulfur Batteries: From Fundamental Research to Practical Application

Yang

Adair

et al. 2018

Electrochem. Energ. Rev.

329

206

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Lithium-sulfur (Li-S) batteries have been considered as one of the most promising energy storage devices that have the potential to deliver energy densities that supersede that of state-of-the-art lithium ion batteries. Due to their high theoretical energy density and cost-effectiveness, Li-S batteries have received great attention and have made great progress in the last few years. However, the insurmountable gap between fundamental research and practical application is still a major stumbling block that has hindered the commercialization of Li-S batteries. This review provides insight from an engineering point of view to discuss the reasonable structural design and parameters for the application of Li-S batteries. Firstly, a systematic analysis of various parameters (sulfur loading, electrolyte/sulfur (E/S) ratio, discharge capacity, discharge voltage, Li excess percentage, sulfur content, etc.) that influence the gravimetric energy density, volumetric energy density and cost is investigated. Through comparing and analyzing the statistical information collected from recent Li-S publications to find the shortcomings of Li-S technology, we supply potential strategies aimed at addressing the major issues that are still needed to be overcome. Finally, potential future directions and prospects in the engineering of Li-S batteries are discussed.

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A Li+-conductive microporous carbon–sulfur composite for Li-S batteries

Cited by 102 publications

References 23 publications

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

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

Preparation of Micropore-rich High Surface Area Activated Carbon from N-doped Carbon Precursor and its Application to Positive Electrode in Lithium-sulfur Battery

Structural Design of Lithium–Sulfur Batteries: From Fundamental Research to Practical Application

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