The effect of a solid electrolyte interphase on the mechanism of operation of lithium–sulfur batteries

Markevich, Elena; Salitra, Gregory; Rosenman, Ariel; Talyosef, Yosef; Chesneau, Frédérick; Aurbach, Doron

doi:10.1039/c5ta04613k

Cited by 91 publications

(99 citation statements)

References 42 publications

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“…13,29,[37][38][39] In the present section we demonstrate the possibility of QSS type of sulfur cathodes operation both for carbon with pore width lower than 1 nm and for carbon having more than 50% of their pores wider than 1 nm.…”

Section: Sub-nano Confinement Of Sulfur In Carbon Matrix Is Not a Necmentioning

confidence: 65%

“…Voltage hysteresis and irreversible capacity observed during the first cycles are the result of side reactions of electrolyte solution components with Li 2 S n leading to SEI formation on the surface of S/C composite electrodes, what prevents further irreversible reactions. This scenario was observed also for porous carbons with pores size up to 2-3 nm 29,38,39 which can accommodate not only S 2-4 , but also S 5-8 and sulfur molecules S n (n > 8). Hence, the small molecules concept is not necessary for the explanation of QSS behavior of S/C cathodes.…”

mentioning

confidence: 62%

“…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. 13,29,[37][38][39] Several explanations for this single-plateau behavior can be found in the literature.1. The formation of special complexes of the sulfur embedded in the fine pores with carbon or surface-bound oxygen.…”

mentioning

confidence: 99%

“…The realization of quasi-solid-state reaction is governed by the formation of solid electrolyte interphase (SEI) on the surface of sulfur cathodes during the initial discharge. 29,[38][39][40] Surface films when formed, force desolvation of Li ions that migrate through them, and hence, induce possible quasi-solid-state operation of the cells. Voltage hysteresis and irreversible capacity observed during the first cycles are the result of side reactions of electrolyte solution components with Li 2 S n leading to SEI formation on the surface of S/C composite electrodes, what prevents further irreversible reactions.…”

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confidence: 99%

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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.

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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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Section: Sub-nano Confinement Of Sulfur In Carbon Matrix Is Not a Necmentioning

confidence: 65%

mentioning

confidence: 62%

mentioning

confidence: 99%

mentioning

confidence: 99%

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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.

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102

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“…6(a)). 21 In other words, we would suggest that a solid phase reaction of Li + with S occurs. 22 On the other hand, AZC-800/2KOH@S62 shows similar characteristics to mesoporous carbon ( Fig.…”

Section: Resultsmentioning

confidence: 93%

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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Effect of the Anion Activity on the Stability of Li Metal Anodes in Lithium‐Sulfur Batteries

Cao

Chen

Han

et al. 2016

Adv Funct Materials

128

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3059wileyonlinelibrary.com of 1672 mAh g −1 and of 3860 mAh g −1 , which lead to very high theoretical specifi c energy (2550 Wh kg −1 ) and energy density (2862 Wh L −1 ) for Li-S batteries. However, the stable operation of the sulfur electrode, which signifi cantly differs from the intercalation mechanism in the traditional cathodes used in Li-ion batteries, still faces a series of barriers, including dissolution of long chain polysulfi des (Li 2 S m , m = 4-8), low utilization of sulfur, large volume expansion, and low Coulombic effi ciency (CE). [ 2 ] Moreover, in the so-called shuttle mechanism, lithium polysulfi des formed during discharge and charge processes will migrate from the cathode to the anode side to react with the metallic Li, leading to serious self-discharge, poor CE, and limited cycle life for Li-S batteries. [ 3 ] To address these critical issues, a variety of strategies have been developed to accommodate sulfur species, [ 4 ] mitigate the dissolution of polysulfi des, [ 5,6 ] and block the shuttle effect. [ 7,8 ] With the signifi cant progress made in the development of composite sulfur cathode materials in Li-S batteries, [ 9 ] the stability of a Li metal anode in Li-S batteries has become one of the more urgent challenges in order to reach the desired long-term stability of Li-S batteries. [ 10 ] A Li metal anode is the preferred anode in Li-S batteries not only because of its ultrahigh specifi c capacity, but also due to its low electrochemical potential (−3.040 V vs standard hydrogen electrode) as well as its light weight (molecular weight 6.94 g mol −1 , density 0.534 g cm −3 ) compared to other metals. [ 11 ] However, the use of Li metal as an anode in nonaqueous electrolyte batteries is challenging because Li often forms dendritic and mossy Li metal deposits during repeated charge/discharge cycles, leading to low CE and a short cycle life, as well as safety concerns. In Li-S batteries, a passivation layer is readily formed on the metallic Li anode surface due to the presence of polysulfi des and electrolyte additives. This layer will lead to increased cell resistance and failure of the Li-S battery. [ 10 ] Various strategies have been developed to minimize the corrosion of Li anodes and to reduce their increase in impedance under operating conditions, including the use of electrolyte additives, [ 12 ] co-solvent, [ 13 ] polymer electrolytes, [ 14 ] and interlayers. [ 8 ] Recently, concentrated electrolytes were demonstrated Effect of the Anion Activity on the Stability of Li Metal Anodes in Lithium-Sulfur BatteriesRuiguo Cao , Junzheng Chen , Kee Sung Han , Wu Xu , Donghai Mei , Priyanka Bhattacharya , Mark H. Engelhard , Karl T. Mueller , Jun Liu , and Ji-Guang Zhang * With the signifi cant progress made in the development of cathodes in lithium-sulfur (Li-S) batteries, the stability of Li metal anodes becomes a more urgent challenge in these batteries. Here the systematic investigation of the stability of the anode/electrolyte interface in Li-S batteries with concentrated ele...

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The effect of a solid electrolyte interphase on the mechanism of operation of lithium–sulfur batteries

Cited by 91 publications

References 42 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

Effect of the Anion Activity on the Stability of Li Metal Anodes in Lithium‐Sulfur Batteries

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