Recent progress and remaining challenges in sulfur-based lithium secondary batteries – a review

Bresser, Dominic; Passerini, Stefano; Scrosati, B.

doi:10.1039/c3cc46131a

Cited by 477 publications

(379 citation statements)

References 193 publications

Supporting

Mentioning

373

Contrasting

Unclassified

Order By: Relevance

“…The great majority of publications on Li-S batteries are devoted to study and development of Li-S electrodes which behave according to this solid-liquid-solid reaction path. 4,6,11,12 * Electrochemical Society Fellow. z E-mail: markeve@mail.biu.ac.il; salitrg@biu.ac.il; doron.aurbach@biu.ac.il However, in several works another type of behavior of Li-S electrodes was described.…”

Section: -10mentioning

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

View full text Add to dashboard Cite

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 ...

show abstract

Section: -10mentioning

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

View full text Add to dashboard Cite

show abstract

“…However, current Li-ion batteries using electrodes based on Li þ -ion insertion chemistry cannot satisfy this demand in terms of specific energy 1,2 . Elemental sulphurabundant and nontoxic-has become one of the most promising positive electrode active materials because of its high theoretical specific capacity (1,675 mAh g À 1 ), based on a redox reaction that reversibly interconverts sulphur and Li 2 S via intermediate lithium polysulphides (LiPSs, that is, Li 2 S n with n ¼ 4-8) [3][4][5] . Li-S cells generally experience low sulphur utilization and poor long-term cycling mainly because of three factors: poor conductivity of sulphur and its discharge products, a large volumetric expansion upon the formation of Li 2 S, and the dissolution of LiPS intermediates in liquid electrolytes, which triggers a polysulphide-shuttle process [3][4][5] .…”

mentioning

confidence: 99%

Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries

et al. 2014

View full text Add to dashboard Cite

The lithium-sulphur battery relies on the reversible conversion between sulphur and Li 2 S and is highly appealing for energy storage owing to its low cost and high energy density. Porous carbons are typically used as sulfur hosts, but they do not adsorb the hydrophilic polysulphide intermediates or adhere well to Li 2 S, resulting in pronounced capacity fading. Here we report a different strategy based on an inherently polar, high surface area metallic oxide cathode host and show that it mitigates polysulphide dissolution by forming an excellent interface with Li 2 S. Complementary physical and electrochemical probes demonstrate strong polysulphide/Li 2 S binding with this 'sulphiphilic' host and provide experimental evidence for surface-mediated redox chemistry. In a lithium-sulphur cell, Ti 4 O 7 /S cathodes provide a discharge capacity of 1,070 mAh g À 1 at intermediate rates and a doubling in capacity retention with respect to a typical conductive carbon electrode, at practical sulphur mass fractions up to 70 wt%. Stable cycling performance is demonstrated at high rates over 500 cycles.

show abstract

“…Lithium-sulphur batteries hold the potential to revolutionize the rechargeable energy storage market, since they can potentially deliver a much higher energy than lithium-ion batteries of the same weight [1][2][3][4][5][6][7][8][9][10][11][12]. However, improvements at the level of cell performance are required.…”

Section: Introductionmentioning

confidence: 99%

A simple, experiment-based model of the initial self-discharge of lithium-sulphur batteries

Al-Mahmoud

Dibden

Owen

et al. 2016

Journal of Power Sources

View full text Add to dashboard Cite

One of the main challenges in the development of lithium-sulphur batteries is the so called "shuttle mechanism", which involves the diffusion of sulphur and polysulphides from the sulphur electrode to the lithium electrode, where they get reduced via chemical reactions with lithium. The shuttle mechanism decreases the capacity delivered by the battery, hampers its rechargeability, and promotes battery selfdischarge. We have developed a simple model of the shuttle mechanism that reproduces quantitatively the rate of the initial self discharge of lithium-sulphur batteries. The rate of sulphur and polysulphide diffusion has been quantified by studying cells with varying number of separators between the electrodes. We have found that it is essential that the model incorporates the presence of carbon additive in the sulphur electrode, which slows down the decrease of the open circuit potential with time. The model also reproduces well the rate of self-discharge of lithium-sulphur cells containing sulphur dissolved in the electrolyte. In conclusion, the present model provides a basic 2 understanding of the mechanism of self-discharge of lithium-sulphur cells, and allows quantifying the two main causes of sulphur loss at the sulphur electrode: sulphur diffusion across a concentration gradient and sulphur reaction with polysulphides formed at the lithium electrode.

show abstract

Recent progress and remaining challenges in sulfur-based lithium secondary batteries – a review

Cited by 477 publications

References 193 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?

Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries

A simple, experiment-based model of the initial self-discharge of lithium-sulphur batteries

Contact Info

Product

Resources

About