The use of elemental sulfur as an alternative feedstock for polymeric materials

Chung, Woo Jin; Griebel, Jared J.; Kim, Eui‐Tae; Yoon, Hyunsik; Simmonds, Adam G.; Ji, Hyun; Dirlam, Philip T.; Glass, Richard S.; Wie, Jeong Jae; Nguyen, Ngoc A.; Guralnick, Brett; Park, Jungjin; Somogyi, Árpád; Théato, Patrick; Mackay, Michael E.; Sung, Yung Eun; Char, Kookheon; Pyun, Jeffrey

doi:10.1038/nchem.1624

Cited by 1,197 publications

(1,467 citation statements)

References 27 publications

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“…These C-SLi sites can also provide a precipitation points for the discharged Li2S species. [56] As shown in Figure 3D, two well-defined discharge plateaus are observed, which are assigned to the multistep reduction mechanism of elemental sulfur. The first plateau, centered at around 2.3 V is generally attributed to the reduction of neutral sulfur species and formation of S8 2-.…”

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confidence: 84%

Nucleophilic substitution between polysulfides and binders unexpectedly stabilizing lithium sulfur battery

et al. 2017

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Polysulfide shuttling has been the primary cause of failure in lithium-sulfur (Li-S) battery cycling. Here, we demonstrate an uncleophilic substitution reaction between polysulfides and binder functional groups can unexpectedly immobilizes the polysulfides. The substitution reaction is verified by UV-visible spectra and X-ray photoelectron spectra. The immobilization of polysulfide is in situ monitored by synchrotron based sulfur K-edge X-ray absorption spectra. The resulting electrodes exhibite initial capacity up to 20.4 mAh/cm 2 , corresponding to 1199.1 mAh/g based on a micron-sulfur mass loading of 17.0 mg/cm 2 . The micron size sulfur transformed into nano layer coating on the cathode binder during cycling.Directly usage of nano-size sulfur promotes higher capacity of 33.7 mAh/cm 2 , which is the highest areal capacity reported in Li-S battery. This enhance performance is due to the reduced shuttle effect by covalently binding of the polysulfide with the polymer binder.2

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confidence: 84%

Nucleophilic substitution between polysulfides and binders unexpectedly stabilizing lithium sulfur battery

et al. 2017

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“…31 These HOPSs (S n 2 − , n = 8-4) are generated and soluble in the electrolyte; thus, the summation of the upper plateau and slope regions between~2.3 and~2.1 V can be defined as the dissolution region. Once the composition of S 4 2 − is reached, HOPSs are further reduced to low-order polysulfides (LOPSs, (S n 2 − , n = 2 and 1)) in the lower plateau region (~2.1 V), whereas HOPSs are soluble in the electrolyte, LOPSs are precipitated as solid phases. Thus, the lower plateau region can be defined as the precipitation region.…”

Section: Electrochemical Tests For Li-s Batteriesmentioning

confidence: 99%

“…Recently, Li-S batteries that can operate by the reversible electrochemical transformation between sulfur (S 8 ) and dilithium sulfide (Li 2 S) have attracted great attention because they can deliver high energy with a moderate voltage owing to the direct use of elemental lithium and sulfur as an anode and a cathode, respectively. 3 Sulfur generated from petroleum refinement is an ideal choice for a cathode owing to its low cost, environmental friendliness, and high theoretical specific capacity (1675 mAh g − 1 by 16 electron process) when it is fully reduced to Li 2 S. [2][3][4] However, several barriers limit the efficient use of sulfur as a cathode: the deleterious electrochemically induced volume expansion from S 8 to Li 2 S (~80%), the poor electronic conductivities of S 8 (~1 × 10 − 30 S m − 1 ) and Li 2 S (~1 × 10 − 14 S m − 1 ), and the irreversible loss of high-order polysulfides (HOPSs) to the electrolyte. 5,6 In particular, the loss of HOPSs during cycling is responsible for poor cycle stability, low sulfur utilization and the polysulfide-shuttle phenomenon.…”

Section: Introductionmentioning

confidence: 99%

Graphene quantum dots: structural integrity and oxygen functional groups for high sulfur/sulfide utilization in lithium sulfur batteries

et al. 2016

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Lithium-sulfur (Li-S) batteries are expected to overcome the limit of current energy storage devices by delivering high specific energy with low material cost. However, the potential of Li-S batteries has not yet been realized because of several technical barriers. Poor electrochemical performance is mainly attributed to the low electrical conductivity of the fully charged and discharged species, the irreversible loss of polysulfide anions and the decrease in the number of electrochemically active reaction sites during battery operation. Here, we report that the introduction of graphene quantum dots (GQDs) into the sulfur cathode dramatically enhanced sulfur/sulfide utilization, yielding high performance. In addition, the GQDs induced structural integrity of the sulfur-carbon electrode composite by oxygen-rich functional groups. This hierarchical architecture enabled fast charge transfer while minimizing the loss of lithium polysulfides, which is attributed to the physicochemical properties of GQDs. The mechanisms through which excellent cycling and rate performance are achieved were thoroughly studied by analyzing capacity versus voltage profiles. Furthermore, experimental observations and theoretical calculations further clarified the role played by GQDs by proving that C-S bonding occurs. Thus, the introduction of GQDs into Li-S batteries will provide an important breakthrough allowing their use as high-performance and low-cost batteries for next-generation energy storage systems. INTRODUCTIONRechargeable lithium-ion batteries are widely used in various applications, such as portable devices, bio-medical implants and electric vehicles, because of their high energy and power density. 1,2 However, current lithium-ion batteries based on the graphite and transition metal oxide couple have nearly reached their ceiling with respect to storage capability because of the limitations associated with their electrical properties and crystal structure. Therefore, breakthroughs in new energy storage systems that can surpass the current performance barrier of lithium-ion batteries should be brought about in a timely manner. Recently, Li-S batteries that can operate by the reversible electrochemical transformation between sulfur (S 8 ) and dilithium sulfide (Li 2 S) have attracted great attention because they can deliver high energy with a moderate voltage owing to the direct use of

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“…Sulfide, which is a common and undesirable water pollutant [26,27], has been selected as an efficient sacrificial electron-donating solute. In addition to the sulfide anion, its conjugated acid hydrogen sulfide is a large scale by-product in petrochemical processing [28,29] (where it is converted to elemental sulfur for disposal), and uses thereof are intensively sought as a desirable strategy for its valorisation as a feedstock [30]. The possibility of using sulfide species as sacrificial electron donors for the photocatalytic production of fuels has been extensively studied mostly on metal sulfide semiconductors, although these processes often require additional solutes such as sulfite to prevent photocorrosion [27][28][29].…”

Section: Introductionmentioning

confidence: 99%

Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H2 from aqueous sulfide

Gonell

Puga

Julián‐López

et al. 2016

Applied Catalysis B: Environmental

110

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Copper-doped titanium dioxide materials with anatase phase (Cu-TiO 2 , atomic Cu contents ranging from 0 to 3% relative to the sum of Cu and Ti), and particle sizes of 12-15 nm, were synthesised by a solvo-thermal method using ethanol as the solvent and small amounts of water to promote the hydrolysis-condensation processes. Diffuse reflectance UV-vis spectroscopy show that the edges of absorption of the titania materials are somewhat shifted to higher wavelengths due to the presence of Cu. X-Ray Photoelectron Spectroscopy (XPS) indicate that Cu(II) is predominant. Photocatalytic CO 2 reduction experiments were performed in aqueous Cu-TiO 2 suspensions under UV-rich light and in the presence of different solutes. Sulfide was found to promote the efficient production of H 2 from water and formic acid from CO 2 . The effect of the Cu content on the photoactivity of Cu-TiO 2 was also studied, showing that copper plays a role on the photocatalytic reduction of CO 2 . IntroductionCarbon dioxide is an inexpensive and widely available feedstock. Its use for the production of chemicals is doubly beneficial, since in addition to its availability, it would represent a decrease in the carbon footprint for the manufacturing of the particular chemical. Other researchers have reported lower but noticeable methanol yields using similarly prepared photocatalysts and Hg lamp irradiation (10-23 µmol g cat −1 h −1 ) [19,20]. In gas-phase reactions, the formation of methanol was also reported, but in considerably lower yields (2 nmol g cat −1 h −1 ), being methane the major product formed by Cu/TiO 2 photocatalysis [21]. In contrast, similar materials were found to promote the formation of several hydrocarbons including methane, ethane and ethylene in conjunction with larger amounts of H 2 [22], whereas CO and methane were major products found in a more recent study [23]. A significant degree of discrepancy regarding the identity of the reaction products (in addition to their selectivities and yields) is apparent by considering the aforementioned literature data, although this could be in part due to the different synthetic procedures used for the preparation of the photocatalysts and to the varied irradiation conditions used.Despite the notable progress in this field of research, there is no clear trend which may allow to conclude on the actual mechanistic route and to gain knowledge on the role of copper on the reaction. Thorough kinetic and in situ spectroscopic studies would provide valuable information on the reaction at the surface of the photocatalyst and may guide future design of more active copper-titania materials. An important issue to focus on is the possible back-reactions of the reduction products on the photocatalyst. For example, it was observed that methanol and formaldehyde, initially formed by a photocatalytic process using Cu(0) powder and TiO 2 , were 3 rapidly consumed by in situ formed Cu/TiO 2 [24]. The simultaneous occurrence of CO 2 reduction and decomposition of the products should result in stat...

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The use of elemental sulfur as an alternative feedstock for polymeric materials

Cited by 1,197 publications

References 27 publications

Nucleophilic substitution between polysulfides and binders unexpectedly stabilizing lithium sulfur battery

Nucleophilic substitution between polysulfides and binders unexpectedly stabilizing lithium sulfur battery

Graphene quantum dots: structural integrity and oxygen functional groups for high sulfur/sulfide utilization in lithium sulfur batteries

Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H2 from aqueous sulfide

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