In-situ X-ray diffraction studies of lithium–sulfur batteries

Cañas, Natalia A.; Wolf, Steffen; Wagner, Norbert; Friedrich, K. Andreas

doi:10.1016/j.jpowsour.2012.10.092

Cited by 202 publications

(227 citation statements)

References 17 publications

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“…Analogous to our study, the formation of large crystalline sulfur domains at the cathode/separator interface upon charging of a discharged sulfur electrode was also observed by Cañas et al, 38 albeit with different shapes/morphology. We believe that the accumulation of sulfur at the cathode/separator interface during the last stages of the charging process is most likely due to the oxidation of dissolved polysulfides (solubilities of 0.1 to 1 mol/l in the electrolyte) contained inside the separator (rather than inside the cathode) during the final stages of charging: under this condition, the high cathode potential will cause the rapid and highly localized oxidation of polysulfides which are stored inside the separator region once they reach the cathode/separator interface, thereby forming a deposit at this very interface.…”

Section: Activation Of LI 2 S In Lisupporting

confidence: 90%

“…5b). This may be compared to the study by Cañas et al, 38 who observed the disappearance of Li 2 S diffractions during the charge of a discharged S cathode at already ≈50% of the charging capacity, which is most likely due to the much smaller Li 2 S particles formed during S [a] SEM image of the middle separator (out of three layers) of a Li/Li 2 S half-cell after initial charging at 1 C as shown by the red curve in Fig. 3a. [b] EDS mapping of carbon, oxygen, and sulfur of a lithium dendrite feature in the separator, whereby the high oxygen signal at the location of the dendrite originates from lithium which was deliberately exposed to air in order to oxidize it.…”

Section: Activation Of LI 2 S In Limentioning

confidence: 94%

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Li-S Batteries with Li₂S Cathodes and Si/C Anodes

Jha

Buchberger

Cui

et al. 2015

J. Electrochem. Soc.

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Lithium-sulfur (Li-S) batteries promise improved capacities over lithium ion batteries. While currently mostly metallic lithium anodes are used, the use of silicon-anodes might offer better safety and durability. However, in a lithium-sulfur-Silicon (Li-S-Si) battery, lithium must be introduced either on the anode or on the cathode in form of Li 2 S. In this study, we have prepared Li 2 S cathodes in combination with Si anodes (i.e., Si/Li 2 S full-cells) to investigate both the processes during initial charging/activation of Li 2 S cathodes and the effect of Li 2 S cathode activation on the cycling performance of Si/Li 2 S full-cells. We observed that the initial activation requires a substantially higher charging potential than for the subsequent cycles. In situ XRD analysis of the cathode during the first cycle clearly indicates the gradual transformation of Li 2 S to polysulfides and finally to crystalline sulfur, i.e., even large Li 2 S particles (≈20 μm) can be charged completely. The result is further confirmed by ex-situ SEM/EDS analysis, which revealed the formation of large sheets of sulfur at the cathode/separator interface. Similar cycling performance of Si/Li 2 S full-cells is observed at both 0.1 C and 1 C rates, a clear advantage over Li/Li 2 S cells, which suffer from severe dendrite formation at 1 C in the case of high Li 2 S loadings. High capacity energy storage systems are needed for various applications ranging from portable electronic devices to automotive applications. For the latter, a safe onboard energy storage system that can provide sufficient driving range is needed. However, the specific energy of current intercalation based lithium ion batteries (≈250-280 Wh/kg cell ) substantially limits the driving range compared to that of conventional fuel vehicles 1,2 so that batteries offering higher specific energy are required.Lithium-air (Li-O 2 ) 3 and lithium-sulfur (Li-S) 4,5 batteries are among the most widely explored so-called post-lithium ion technologies, for which the lithium ions in the cathode react with either oxygen or sulfur during discharge, resulting in Li 2 O 2 or Li 2 S discharge product, respectively. Considering the high theoretical specific energy of these post-lithium ion cathodes on the active materials level (viz., ≈3.5 kWh/kg Li2O2 for Li-O 2 and ≈2.5 kWh/kg Li2S for Li-S 1 ), they are very promising for use in electric vehicles, even though the specific energy gains over lithium ion batteries if compared on the battery system level are substantially lower. 6 However, there are still several major issues to be resolved. In the case of Li-O 2 batteries, these include the poor charge/discharge reversibility 7,8 as well as the poor stability of electrolytes 9-11 and of the catalyst support. 12 Similarly, Li-S batteries are still plagued by an irreversible loss of active sulfur species, by polysulfide shuttling, and by the continuous electrolyte consumption at the lithium electrode.13,14 Nevertheless, Li-S battery performance/durability has improved significantly over ...

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Section: Activation Of LI 2 S In Lisupporting

confidence: 90%

Section: Activation Of LI 2 S In Limentioning

confidence: 94%

Li-S Batteries with Li₂S Cathodes and Si/C Anodes

Jha

Buchberger

Cui

et al. 2015

J. Electrochem. Soc.

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“…The cathode electrolytes consisted of 10 µL of sulfolane containing 10 mM of the relevant POM and 1 M LiTFSI, as sulfolane allowed stable operation at high temperatures due to its high boiling point (>280°C) while ether-based liquid electrolytes would not. 6,12,[21][22][23][24][25] Hence, each cell contained 0.1 µmol of POM and approximately 28 µmol of sulfur atoms. A standard electrolyte that did not contain POM was also used as a control sample.…”

Section: Cell Preparation With Protective Anodementioning

confidence: 99%

“…The second section of the discharge curves is the low voltage region (Q low ), comprised of a well-defined plateau where less soluble Li 2 S 2 and Li 2 S are produced (theoretically, Q low = 1256 mAh g ¹1 ). [21][22][23][24][25] Analyzing the discharge curves focusing on the capacities in high and low voltage regions provides further insights into the effects of SiW on the sulfur redox chemistry at the cathode. For the cell containing SiW, Q high and Q low were 420 mAh g ¹1 and 860 mAh g ¹1 , respectively (Fig.…”

Section: ¹1mentioning

confidence: 99%

Keggin-type Polyoxometalates as Bidirectional Redox Mediators for Rechargeable Batteries

Choi

Park

et al. 2016

Electrochemistry

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Keggin-type polyoxometalates (POMs), which possess multiple redox centers, were investigated as bidirectional redox mediators in rechargeable batteries. A series of POMs have been synthesized and employed in sulfur electrodes where neither the active material nor the discharge product were electrically conductive. POMs were found to have multiple redox potentials covering the range of the equilibrium potentials of the redox reactions of sulfur, which consequently facilitated both charge and discharge reactions. In particular, [SiMo 12 O 40 ] 4− offered a large discharge capacity of 1270 mAh g −1 by accelerating the reduction of shorter, less soluble polysulfides, leading to a higher cycling performance. The mediator role was confirmed via an X-ray photoelectron spectroscopy study on the cycled cathodes. Density functional theory calculations showed that the redox potentials of POMs are tunable, allowing selective design of suitable POM molecules for specific battery electrodes.

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“…In the recent years, many review articles are available in the literature describing the working principles, advantages, and limitations of lithium/sulfur batteries (Ji and Nazar, 2010;Barghamadi et al, 2013;Bresser et al, 2013;Manthiram et al, 2013;Nazar and Evers, 2013). Also, numerous articles appear on the fundamental chemistry Zhang, 2013a), performance of modified cathode materials (Ji et al, 2009;Liang et al, 2009;Yang et al, 2011;Fu et al, 2012), their fading mechanism (Diao et al, 2013), AFM, and Raman characterizations (Aurbach et al, 2009;Elazari et al, 2010;Yeon et al, 2012;Hagen et al, 2013) in situ XRD (Canas et al, 2013a) and impedance analysis (Yuan et al, 2009;Canas et al, 2013b). The preparation and characterization of cathode and anode materials for Li-S batteries are beyond the scope of this article.…”

Section: Introductionmentioning

confidence: 99%

Efficient Electrolytes for Lithiumâ€“Sulfur Batteries

Angulakshmi

Stephan

2015

Front. Energy Res.

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This review article mainly encompasses on the state-of-the-art electrolytes for lithiumsulfur batteries. Different strategies have been employed to address the issues of lithiumsulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium-sulfur batteries. The electrolytes for lithium-sulfur batteries are broadly classified as (i) non-aqueous liquid electrolytes, (ii) ionic liquids, (iii) solid polymer, and (iv) glass-ceramic electrolytes. This article presents the properties, advantages, and limitations of each type of electrolytes. Also, the importance of electrolyte additives on the electrochemical performance of Li-S cells is discussed.

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In-situ X-ray diffraction studies of lithium–sulfur batteries

Cited by 202 publications

References 17 publications

Li-S Batteries with Li₂S Cathodes and Si/C Anodes

Li-S Batteries with Li₂S Cathodes and Si/C Anodes

Keggin-type Polyoxometalates as Bidirectional Redox Mediators for Rechargeable Batteries

Efficient Electrolytes for Lithiumâ€“Sulfur Batteries

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In-situ X-ray diffraction studies of lithium–sulfur batteries

Cited by 202 publications

References 17 publications

Li-S Batteries with Li2S Cathodes and Si/C Anodes

Li-S Batteries with Li2S Cathodes and Si/C Anodes

Keggin-type Polyoxometalates as Bidirectional Redox Mediators for Rechargeable Batteries

Efficient Electrolytes for Lithiumâ€“Sulfur Batteries

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Product

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Li-S Batteries with Li₂S Cathodes and Si/C Anodes

Li-S Batteries with Li₂S Cathodes and Si/C Anodes