In situ preparation of CuS cathode with unique stability and high rate performance for lithium ion batteries

Wang, Yourong; Zhang, Xianwang; Chen, Peng; Liao, Hantao; Cheng, Siqing

doi:10.1016/j.electacta.2012.07.004

Cited by 137 publications

(81 citation statements)

References 26 publications

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“…13,15 It has been reported that the higher voltage plateau at 2.1 V corresponds to the lithium insertion into CuS with the initial formation of Li x CuS (equations 1 and 2), while the lower voltage plateau at 1.7 V is related to the conversion reaction to the composite of Li 2 S and Cu (Equation 3). 15 In the second voltage plateau region, factors such as volume change during cycling, electrolyte decomposition and loss of active material due to the solubility of sulfide species contribute to the capacity degradation upon repeated cycling.…”

Section: Resultsmentioning

confidence: 99%

“…9,10 CuS is a promising cathode material for lithium ion batteries due to its high theoretical capacity (560 mAh g −1 ) and flat discharge curve. 11,12 Specific discharge capacities up to 506 mAh g −1 have been demonstrated at the first cycle with good capacity retention over hundreds of cycles, 13,14 which is on the high-end of capacity in the full spectrum of different transition metal sulfides. It should be noted that many transition metal sulfides, 9,16 including CuS, 6 can react with lithium metal at voltages in the vicinity of the working voltage (∼2.1 V) of Li-S battery, providing the opportunity for additional capacity.…”

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confidence: 99%

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Interaction of CuS and Sulfur in Li-S Battery System

Sun

Zhang

et al. 2015

J. Electrochem. Soc.

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The Lithium-Sulfur (Li-S) battery has been a subject of intensive research in recent years due to its potential to provide much higher energy density and lower cost than the current state of the art lithium-ion battery technology. In this work, we have investigated Cupric Sulfide (CuS) as a capacity-contributing conductive additive to the sulfur electrode in a Li-S battery. Galvanostatic charge/discharge cycling has been used to compare the performance of both sulfur electrodes and S:CuS hybrid electrodes with various ratios. We found that the conductive CuS additive enhanced the utilization of the sulfur cathode under a 1C rate discharge. However, under a C/10 discharge rate, S:CuS hybrid electrodes exhibited lower sulfur utilization in the first discharge and faster capacity decay in later cycles than a pure sulfur electrode due to the dissolution of CuS. The CuS dissolution is found to be the result of strong interaction between the soluble low order polysulfide Li 2 S 3 and CuS. We identified the presence of conductive copper-containing sulfides at the cycled lithium anode surface, which may degrade the effectiveness of the passivation function of the solid-electrolyte-interphase (SEI) layer, accounting for the poor cycling performance of the S:CuS hybrid cells at low rate. The Li-S battery is amongst the most promising alternatives to Li-ion batteries, which are approaching their limits in energy density and power capability as determined by the metal oxide based cathode and graphite based anode materials.1 In spite of their high theoretical energy density (2450 Wh kg −1 ), Li-S battery systems under development still suffer from low power, low energy utilization and low efficiency due to factors such as the insulating nature of both sulfur and lithium sulfide, active material dissolution and the well-known shuttling effect.2 Successful remedies to these issues generally involved the use of novel sulfur-carbon cathode architectures.3-5 Meanwhile, transition metal sulfides have also been studied intensively as electrode materials in Li batteries in parallel to sulfur, because they serve as a good compromise between the high energy density of sulfur and better electronic conductivity in combination with a lower solubility of a metal based compound.6-8 Since their electronic conductivities are close to or even exceeding that of graphite (1000 S cm −1 ), these transition metal sulfides can work as conductive fillers for sulfur electrodes as good as carbon black and further contribute additional capacity to the existing Li-S battery to partially balance its fast capacity decay. 9,10 CuS is a promising cathode material for lithium ion batteries due to its high theoretical capacity (560 mAh g −1 ) and flat discharge curve.11,12 Specific discharge capacities up to 506 mAh g −1 have been demonstrated at the first cycle with good capacity retention over hundreds of cycles, 13,14 which is on the high-end of capacity in the full spectrum of different transition metal sulfides. It should be noted that many transition me...

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Interaction of CuS and Sulfur in Li-S Battery System

Sun

Zhang

et al. 2015

J. Electrochem. Soc.

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“…• C. 34 A copperstabilized sulfur-microporous carbon (MC-Cu-S) composite with a high S loading of 50% is synthesized by uniformly dispersing 10% highly electronically conductive Cu nanoparticles into microporous carbon (MC) followed by wet-impregnating S, and is reported as a cathode for carbonate electrolyte Li-S batteries. In the composite of MC-Cu-S, the microporous structure of the MC physical confines the S, while the Cu nanoparticles anchored in the MC further chemically interact with S/polysulfides through Cu-polysulfides CuS x , thereby resulting in a more effective reduction in the active material loss on prolonged cycling.…”

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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“…[8,9] However, they usually suffer from poor capacity retention upon cycling and/or poor rate capability, which is caused by the volume change during cycling, the instability of the carbonate-type electrolyte, and the loss of active material due to dissolution of sulfide species. [10][11][12] One generally accepted strategy to alleviate these problems is to prepare nanometer-sized materials with designed structure. [9,11,13] One-dimensional (1D) nanostructures have attracted a considerable attention as it allows for better accommodation of volume change during repeated charge-discharge.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of One‐Dimensional Copper Sulfide Nanorods as High‐Performance Anode in Lithium Ion Batteries

Shi

et al. 2014

ChemSusChem

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Nanorod-like CuS and Cu2 S have been fabricated by a hydrothermal approach without using any surfactant and template. The electrochemical behavior of CuS and Cu2 S nanorod anodes for lithium-ion batteries reveal that they exhibit stable lithium-ion insertion/extraction reversibility and outstanding rate capability. Both of the electrodes exhibit excellent capacity retentions irrespective of the rate used, even at a high current density of 3200 mA g(-1) . More than 370 mAh g(-1) can be retained for the CuS electrode and 260 mAh g(-1) for the Cu2 S electrode at the high current rate. After 100 cycles at 100 mA g(-1) , the obtained CuS and Cu2 S electrodes show discharge capacities of 472 and 313 mAh g(-1) with retentions of 92% and 96%, respectively. Together with the simplicity of fabrication and good electrochemical properties, CuS and Cu2 S nanorods are promising anode materials for practical use the next-generation lithium-ion batteries.

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In situ preparation of CuS cathode with unique stability and high rate performance for lithium ion batteries

Cited by 137 publications

References 26 publications

Interaction of CuS and Sulfur in Li-S Battery System

Interaction of CuS and Sulfur in Li-S Battery System

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

Synthesis of One‐Dimensional Copper Sulfide Nanorods as High‐Performance Anode in Lithium Ion Batteries

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