Oxidation of Sulfur in Chloroaluminate Melts of Intermediate pCl

Tanemoto, Kei; Marassi, Roberto; Mamantov, C. B.; Ogata, Yoshiro; Matsunaga, M.; Wiaux, J. P.; Mamantov, G.

doi:10.1149/1.2123482

Cited by 15 publications

(7 citation statements)

References 28 publications

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“…The development of various aluminum–sulfur systems began in the 1980s. A nonaqueous aluminum–sulfur system was investigated by Marassi et al in 1977, while the aqueous aluminum–sulfur battery was initially proposed in 1993 by Licht et al Recently, Cohn et al proposed the first aluminum–sulfur cell fabricated using an aluminum‐metal anode and room‐temperature ionic liquid electrolyte of AlCl 3 in 1‐ethyl‐3‐methylimidazolium chloride and a sulfur/carbon composite cathode. This system can reach a high capacity of 1600 mA h g −1 and shows the potential to be electrochemically reversible .…”

Section: Metal–sulfur Cellsmentioning

confidence: 99%

Current Status and Future Prospects of Metal–Sulfur Batteries

Chung¹,

Manthiram²

2019

Advanced Materials

496

415

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that makes use of intercalation materials as the electrodes (Figure 1), applications involving electric vehicles and smart grids may require rechargeable batteries with new battery chemistries that can generate even higher energy densities for longer driving ranges and higher energy-storage capabilities. [6][7][8] Additionally, the lithiated transition-metal oxides used in commercial lithium-ion battery cathodes tend to be expensive, scarce, or toxic to the environment. Thus, it is desirable to explore new electrode materials that are naturally abundant (and therefore less expensive) as well as environmentally compatible in order to successfully enter the future battery markets. [6,[8][9][10][11] This driving force has promoted the development of batteries with conversionreaction electrodes, in which reversible electrochemical reactions take place and new chemical compounds form during the cycling of the battery. Naturally abundant materials, such as sulfur for the cathode, can be applied as electrodes. Different metallic anodes have shown great potential in coupling with sulfur cathode to generate a high energy density, including lithium metal [3,10,[12][13][14][15][16][17]31] as well as other alkali [18][19][20][21][22][23][24]31] and high-valent metals. [18,[25][26][27][28][29][30][31] As a next-generation energy-storage technology beyond lithium-ion batteries, lithium-sulfur batteries are the most promising low-cost, high-capacity energy-storage device available due to their high charge-storage capacity, low cost, and the wide availability of sulfur. [32][33][34][35] The electrochemical reactions of lithium-sulfur batteries involve reversible conversions between sulfur (S 8 ), lithium polysulfides (Li 2 S x , x = 4-8), and lithium sulfides (Li 2 S 2 and Li 2 S). [33][34][35][36] The conversions between sulfur and lithium polysulfides and lithium sulfides involve phase changes between liquid-state polysulfides and solid-state sulfur and sulfides. [35][36][37][38][39][40] Thus, the conversion reaction of lithium-sulfur battery chemistry has no restriction in maintaining the initial crystal chemistry of the electrode during electrochemical cycling. [39][40][41][42] Therefore, a full twoelectron redox reaction per sulfur atom can occur in a manner that is both reversible and stable, increasing the chargestorage capacity drastically as compared to the currently used insertion-reaction oxide cathodes. [7,[39][40][41][42] As a result, sulfur cathodes possess a high theoretical charge-storage capacity of 1672 mA h g −1 , which is the highest value among solid-state Lithium-sulfur batteries are a major focus of academic and industrial energystorage research due to their high theoretical energy density and the use of low-cost materials. The high energy density results from the conversion mechanism that lithium-sulfur cells utilize. The sulfur cathode, being naturally abundant and environmentally friendly, makes lithium-sulfur batteries a potential next-generation energy-storage technology. The current state of the rese...

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Section: Metal–sulfur Cellsmentioning

confidence: 99%

Current Status and Future Prospects of Metal–Sulfur Batteries

Chung¹,

Manthiram²

2019

Advanced Materials

496

415

View full text Add to dashboard Cite

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“…[36,37] Note that certain complex ions (e.g., S 2 Cl + and SCl 3 + ) can more likely exist rather than molecules with the same formula (e.g., S 2 Cl and SCl 3 ). [32][33][34][35]38] Various sulfur chloride species have been checked, and the signals of S 2 Cl + (S 1+ ), S 2 Cl 2 (S 1+ ), SCl 2 (S 2+ ), S 2 Cl 3 (S 1.5+ ), SCl 3 + (S 4+ ), SCl 4 (S 4+ ), and SCl 3 •AlCl 4 (S 4+ ) are displayed in Figure 2a. Among these moieties, S 2 Cl 2 and S 2 Cl + have the strongest and second strongest intensities, respectively, both of which are at the S 1+ state.…”

Section: Resultsmentioning

confidence: 99%

“…[23] On the other hand, the electrochemical mechanism of the Al-S battery is still vague owing to the complicated S oxidation. [32][33][34][35] Recently, a series of characterizations including X-ray diffraction (XRD) and advanced spectroscopies have been employed, demonstrating that the S 4+ state, AlSCl 7 (SCl 3 •AlCl 4 ), is the main electrochemical oxidation product of S in the AlCl 3 /carbamide electrolyte. [29] However, possible liquid products may be less informative owing to their weakened sensitivity to these characterizations.…”

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confidence: 99%

High‐Voltage Aluminium‐Sulfur Batteries with Functional Polymer Membrane

Zhang

Chu

Wang

et al. 2022

Adv Funct Materials

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A high-voltage aluminium-sulfur (Al-S) battery is developed by employing the reversible electrochemical oxidation of S, favoring a high discharge voltage of around 1.8 V (vs Al 3+ /Al). The reversible multiple-electron transformation between positive-and negative-valence S compounds is further realized for activating a high-capacity Al-S battery. The formation of sulfur chlorides as charge products of S, including S 2 Cl 2 (l) as the dominant one, has been clearly identified. Benefiting from a functional polymer membrane infiltrated with AlCl 3 /acetamide electrolyte, which can suppress unwanted electrolyte reactions, restrict the shuttling of sulfur chlorides across the separator, and stabilize the Al anode against degradation, the Al-S battery can deliver largely enhanced performance, with a capacity of 861 mAh g −1 , capacity retentions of 92.1%/79.0% within 50/200 cycles, and durability of 490 cycles. The new electrochemistry scenarios shed light on the development of S-based secondary batteries with higher energy densities for future.

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“…Investigations of Al-S batteries date back to the 1980s, when Marassi et al 20 , 21 studied sulfur in NaCl-AlCl 3 electrolyte melts. A second attempt was undertaken in 1993 by Licht and Peramunage using an aqueous alkaline electrolyte 22 .…”

Section: Historical Aspectsmentioning

confidence: 99%

Advances and challenges of aluminum–sulfur batteries

2022

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The search for cost-effective stationary energy storage systems has led to a surge of reports on novel post-Li-ion batteries composed entirely of earth-abundant chemical elements. Among the plethora of contenders in the ‘beyond lithium’ domain, the aluminum–sulfur (Al–S) batteries have attracted considerable attention in recent years due to their low cost and high theoretical volumetric and gravimetric energy densities (3177 Wh L−1 and 1392 Wh kg−1). In this work, we offer an overview of historical and present research pursuits in the development of Al–S batteries with particular emphasis on their fundamental problem—the dissolution of polysulfides. We examine both experimental and computational approaches to tailor the chemical interactions between the sulfur host materials and polysulfides, and conclude with our view on research directions that could be pursued further.

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Oxidation of Sulfur in Chloroaluminate Melts of Intermediate pCl

Cited by 15 publications

References 28 publications

Current Status and Future Prospects of Metal–Sulfur Batteries

Current Status and Future Prospects of Metal–Sulfur Batteries

High‐Voltage Aluminium‐Sulfur Batteries with Functional Polymer Membrane

Advances and challenges of aluminum–sulfur batteries

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