A structural study of disordered sulfur overlayers on Cu(111)

Rousseau, Gilles; Mulligan, Andrew; Bovet, N.; Adams, Michael E.; Dhanak, Vin; Kadodwala, Malcolm

doi:10.1016/j.susc.2005.12.012

Cited by 16 publications

(21 citation statements)

References 21 publications

(32 reference statements)

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“…25 Mobile Cu and S containing moieties (specifically Cu 3 S 3 ) can be responsible for the significant material transport observed during the adsorption of sulfur on Cu (111). 26 This may be attributed as the reason as to why sulfides are detected in XPS measurement (for surface layer), although elemental S is mainly detected in XRD measurement (for bulk phase structure). The powders are removed from the current collectors to eliminate the disturbance of Cu 0 from the Cu current collector.…”

Section: Resultsmentioning

confidence: 99%

Application of a Sulfur Cathode in Nucleophilic Electrolytes for Magnesium/Sulfur Batteries

Zeng

Wang

Yang

et al. 2017

J. Electrochem. Soc.

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We report the potential feasibility of a high-capacity and low-cost sulfur cathode that is compatible with nucleophilic electrolytes for Mg/S batteries. The electrochemical performance of sulfur in an easily prepared (PhMgCl) 2 -AlCl 3 /THF nucleophilic electrolyte depends on cathode current collectors. A sulfur cathode that uses Cu as a current collector, which is electrochemically stable in the range of operating voltage, exhibits an initial discharge capacity approximately corresponding to 659 mAh g −1 , and maintains a reversible capacity of 113 mAh g −1 after 20 cycles at a current density of 10 mA g −1 . It is different from the sulfur cathode with few capacities that uses stainless-steel as a current collector. Copper sulfides formed when sulfur is coated on a Cu current collector at 50 • C provide a strong chemical interaction between Cu and sulfur, which protects sulfur and increases its compatibility with the electrolyte. A metal-stabilized sulfur cathode provides an effective approach to improve the electrochemical performance of Mg/S batteries in nucleophilic electrolytes. There is a constant increase in the demand for low-cost, highenergy-density rechargeable batteries that utilize environmentally friendly elements for applications, such as market-competitive electric vehicles and large-scale power storage systems due to fossil energy shortage and environmental issues. Following the rapid development of electric vehicles with space available to mount battery packs, it is now necessary for batteries to possess good safety characteristics 1 and high volumetric energy density, which is more important than gravimetric energy density.2 Rechargeable magnesium batteries with magnesium as the anode may correspond to superior candidates compatible with post Li-ion batteries that contain a lithium metal anode, which provides a volumetric capacity (2062 mAh cm −3 ) exceeding that of a current graphite anode (777 mAh cm −3 ), 2 due to a relatively lower price ($2700 and $64800/ton for Mg and Li, respectively), 2,3 a higher theoretical volumetric capacity (3832 mAh cm −3 ), 2 and higher expected safety (the dendritic morphologies for magnesium deposits are lower than that for lithium). 4 Muldoon et al. first suggested an electrophilic sulfur cathode candidate with a high theoretical capacity (1671 mAh g −1 or 3459 mAh cm −3 ) corresponding to a conversion class as opposed to an insertion class. It is chemically incompatible with nucleophilic magnesium organohaloaluminate electrolytes and compatible with a non-nucleophilic electrolyte based on a recrystallized Mg complex [Mg 2 (μ-Cl) 3 (THF) 6 ][HMDSAlCl 3 ] formed from a reaction between hexamethyldisilazide magnesium chloride (HMDSMgCl) and AlCl 3 (3:1 molar ratio) in tetrahydrofuran (THF).2,4 The magnesium/sulfur (Mg/S) batteries yield a theoretical volumetric energy density exceeding 4000 Wh L −1 as compared to 2800 Wh L −1 for lithium/sulfur (Li/S) batteries.5 However, on cycling, Mg/S batteries also suffer from capacity fading, which results from low active...

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Section: Resultsmentioning

confidence: 99%

Application of a Sulfur Cathode in Nucleophilic Electrolytes for Magnesium/Sulfur Batteries

Zeng

Wang

Yang

et al. 2017

J. Electrochem. Soc.

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“…Similarly, spectroscopic evidence suggests sulfur promotes binding through the formation of Cu + cations, but can also block hydrocarbon adsorption on more oxidized copper atoms [101]. This evidence may explain some variation in catalysis results, as sulfur preferentially forms a ( √ 7 × √ 7)R19.1°on the Cu(111) surface which has a high (0.43 ML) coverage resulting from introduction of sulfur into the subsurface [102,103], whereas at low coverage surface sulfur forms a more mobile species [104].…”

Section: Sulfurmentioning

confidence: 99%

Surface-level mechanistic studies of adsorbate–adsorbate interactions in heterogeneous catalysis by metals

Marshall

Medlin

2011

Surface Science Reports

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“…A more recent study by Rousseau et al, 80 following on the work of Feibelman and Ling et al, proposed that disordered S/Cu͑111͒ overlayers at room temperature consist of a disordered, equilibrated mixture of sulfur adatoms and Cu 3 S 3 clusters. This conclusion was based on normal incidence x-ray standing wave absorption data.…”

Section: Experimental Evidence For Clusters In S/cu"111…mentioning

confidence: 99%

Adsorbate-enhanced transport of metals on metal surfaces: Oxygen and sulfur on coinage metals

Thiel

Shen

Liu

et al. 2010

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Coarsening (i.e., ripening) of single-atom-high, metal homoepitaxial islands provides a useful window on the mechanism and kinetics of mass transport at metal surfaces. This article focuses on this type of coarsening on the surfaces of coinage metals (Cu, Ag, Au), both clean and with an adsorbed chalcogen (O, S) present. For the clean surfaces, three aspects are summarized: (1) the balance between the two major mechanisms-Ostwald ripening (the most commonly anticipated mechanism) and Smoluchowski ripening-and how that balance depends on island size; (2) the nature of the mass transport agents, which are metal adatoms in almost all known cases; and (3) the dependence of the ripening kinetics on surface crystallography. Ripening rates are in the order (110)>(111)>(100), a feature that can be rationalized in terms of the energetics of key processes. This discussion of behavior on the clean surfaces establishes a background for understanding why coarsening can be accelerated by adsorbates. Evidence that O and S accelerate mass transport on Ag, Cu, and Au surfaces is then reviewed. The most detailed information is available for two specific systems, S/Ag (111) and S/Cu(111). Here, metal-chalcogen clusters are clearly responsible for accelerated coarsening. This conclusion rests partly on deductive reasoning, partly on calculations of key energetic quantities for the clusters (compared with quantities for the clean surfaces), and partly on direct experimental observations. In these two systems, it appears that the adsorbate, S, must first decorate-and, in fact, saturate-the edges of metal islands and steps, and then build up at least slightly in coverage on the terraces before acceleration begins. Acceleration can occur at coverages as low as a few thousandths to a few hundredths of a monolayer. Despite the significant recent advances in our understanding of these systems, many open questions remain. Among them is the identification of the agents of mass transport on crystallographically different surfaces e.g., 111, 110, and 100. KeywordsAmes Laboratory, Materials Science and Engineering, Mathematics, Physics and Astronomy Disciplines Biological and Chemical Physics | Materials Science and Engineering | Mathematics | Physical Chemistry CommentsThe following article appeared in Journal of Vacuum Science and Technology A 28, no. 6 (2010) Coarsening ͑i.e., ripening͒ of single-atom-high, metal homoepitaxial islands provides a useful window on the mechanism and kinetics of mass transport at metal surfaces. This article focuses on this type of coarsening on the surfaces of coinage metals ͑Cu, Ag, Au͒, both clean and with an adsorbed chalcogen ͑O, S͒ present. For the clean surfaces, three aspects are summarized: ͑1͒ the balance between the two major mechanisms-Ostwald ripening ͑the most commonly anticipated mechanism͒ and Smoluchowski ripening-and how that balance depends on island size; ͑2͒ the nature of the mass transport agents, which are metal adatoms in almost all known cases; and ͑3͒ the dependence of the ripe...

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A structural study of disordered sulfur overlayers on Cu(111)

Cited by 16 publications

References 21 publications

Application of a Sulfur Cathode in Nucleophilic Electrolytes for Magnesium/Sulfur Batteries

Application of a Sulfur Cathode in Nucleophilic Electrolytes for Magnesium/Sulfur Batteries

Surface-level mechanistic studies of adsorbate–adsorbate interactions in heterogeneous catalysis by metals

Adsorbate-enhanced transport of metals on metal surfaces: Oxygen and sulfur on coinage metals

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