Chemisorption and electrocatalytic effect from CoxSny alloy for high performance lithium sulfur batteries

Qiao, Zhensong; Zhou, Fan; Zhang, Qingfei; Pei, Fei; Zheng, Hongfei; Xu, Wanjie; Liu, Pengfei; Ma, Yating; Xie, Qingshui; Wang, Laisen; Fang, Xiaoliang; Peng, Dong‐Liang

doi:10.1016/j.ensm.2019.05.032

Cited by 80 publications

(50 citation statements)

References 52 publications

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“…In the Raman spectra (Figure 1g), the broad peaks at 1348 and 1576 cm −1 are assigned to the D and G bands of carbon, respectively. [ 12 ] The intensity ratio of G to D bands ( i G / i D ) for the FeCFeOC composite (≈2.02) is twice higher than that of the porous C material (≈1.05), further evidencing its higher graphitization degree by the catalytic effect from the Fe‐based materials. In addition, the relatively strong peak at 2680 cm −1 results from the 2D band of carbon, suggesting the formation of highly graphitized multilayered carbon, which is similar to the multilayered graphene structure.…”

Section: Resultsmentioning

confidence: 99%

Anchoring Polysulfides and Accelerating Redox Reaction Enabled by Fe‐Based Compounds in Lithium–Sulfur Batteries

Qiao

Zhang

Meng³

et al. 2021

Adv Funct Materials

Self Cite

112

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The synergetic mechanism of chemisorption and catalysis play an important role in developing high‐performance lithium–sulfur (Li–S) batteries. Herein, a 3D lather‐like porous carbon framework containing Fe‐based compounds (including Fe3C, Fe3O4, and Fe2O3), named FeCFeOC, is designed as the sulfur host and the interlayer on separator. Due to the strong chemisorption and catalytic ability of FeCFeOC composite, the soluble lithium polysulfides (LiPSs) are first adsorbed and anchored on the surface of the FeCFeOC composite and then are catalyzed to accelerate their conversion reaction. In addition, the FexOy in Fe‐based compounds can spontaneously react with LiPSs to form magnetic FeSx species with a larger size, further blocking the penetration of LiPSs cross the separator. As a result, the assembled Li–S cells show excellent long‐term stability (748 mAh g−1 over 500 cycles at 1.0 C, and ≈0.036% decay per cycle for 1000 cycles at 3.0 C), a superb rate capability with 659 mAh g−1 at 5.0 C, and lower electrochemical polarization. This work introduces a feasible strategy to anchor and accelerate the conversion of LiPSs by designing the multifunctional Fe‐based compounds with high chemisorption and catalytic activity, which advances the large‐scale application of high‐performance Li–S batteries.

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Section: Resultsmentioning

confidence: 99%

Anchoring Polysulfides and Accelerating Redox Reaction Enabled by Fe‐Based Compounds in Lithium–Sulfur Batteries

Qiao

Zhang

Meng³

et al. 2021

Adv Funct Materials

Self Cite

112

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“…Other materials such as few‐layer phosphorene nanosheets, [ 93 ] hollow Co x Sn y alloy, [ 94 ] and B 4 C nanowire [ 95 ] also show catalytic effect for the promoted electrochemical performances of the high‐loading Li–S batteries. Take the B 4 C nanowire for example, a self‐supported architecture with radially aligned B 4 C‐nanowire array grown on the carbon nanofiber backbone (B 4 C@CNF) was developed.…”

Section: Suppressing Shuttling Of the Intermediatesmentioning

confidence: 99%

Strategies toward High‐Loading Lithium–Sulfur Battery

Chen

Lei

et al. 2020

Advanced Energy Materials

313

176

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despite all these promises, three intrinsic drawbacks need to be resolved before fulfilling the promise of the market potential.First, the most stable but electronically insulating S 8 (≈10 −14 S cm −2 ) with cyclic configuration is used as the starting material in Li-S cathode, significantly limiting the full utilization of the active materials to reach the theoretical capacity. Therefore, it is the first priority to design the cathode that ensures the maximum usage of the starting materials, which sets the upper limit of the capacity performance. Second, the muti-step reduction process releases highly soluble lithium polysulfides (LiPSs) intermediates (Li 2 S x , where x = 4-8) into the organic electrolyte. [6] Unlike the batteries based on ion-insertion mechanism, [7,8] Li-S battery possesses unique and complex electrochemical/chemical processes during operation. During galvanostatic discharge process, two distinct plateaus can be verified at about 2.4 and 2.1 V in the voltage profile, corresponding to the reduction of sulfur into long-chain polysulfides and subsequent reaction from short-chain polysulfides to Li 2 S, respectively. [9] Further investigations about the reaction mechanism of Li-S battery based on experimental and theoretical studies reveal that the existence of various intermediates during electrochemical processes, indicating much more complex battery chemistry compared to the simple stepwise reaction model. [10,11] As a result, the soluble intermediates can diffuse through the polymeric separator to the anode surface, causing the loss of active materials and degradation of anode. Third, the density difference between the starting material (sulfur, 2.07 g cm −3 ) and discharge product (Li 2 S, 1.66 g cm −3 ) causes significant volumetric change during continuous cycling, damaging the integrity of the cathode structure and leading to serious capacity fading. [12] Besides above problems concerning the cathode side of the Li-S battery, other issues arose on the anode side, such as the unstable solid-electrolyte interphase (SEI), surface passivation, and uncontrolled lithium dendrite growth. [13][14][15] Stemmed from the basic problems mentioned above from the very beginning of the designed Li-S battery systems, various derivative problems were gradually unraveled during persistent efforts for improving the battery performance to approach the ultimate goal for commercialization. In the past decade, fundamental studies about Li-S battery were carried in laboratories all over the world, and it gradually put the puzzle together while brought promising performance improvement. [11,[16][17][18][19][20] However, to date, most of the lab-scale progresses have been based on batteries with sulfur loading lower than 2 mg cm −2 , Lithium-sulfur (Li-S) batteries, due to the high theoretical energy density, are regarded as one of the most promising candidates for breaking the limitations of energy-storage system based on Li-ion batteries. Tremendous efforts have been made to meet the challenge of high-performan...

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“…[ 28,29 ] Notwithstanding these advances, few studies have attempted to explore bimetallic alloying electrocatalyst toward polysulfide management, where persuasive electrochemical investigation and systematic mechanism probing are still lacking. [ 30 ] In further contexts, unlike the extensive attention focused on the liquid–solid polysulfide conversion process, barely no effort has been exerted on studying Li 2 S/Li 2 S 2 oxidation kinetics. [ 31 ] In this case, rational design of electrocatalysts for boosting the bidirectional catalytic activity is of paramount significance to deepen the understanding of Li–S chemistry.…”

Section: Introductionmentioning

confidence: 99%

Boosting Dual‐Directional Polysulfide Electrocatalysis via Bimetallic Alloying for Printable Li–S Batteries

Shi

Sun

Cai

et al. 2020

Adv Funct Materials

109

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The rational design of electrocatalyst has readily stimulated a burgeoning interest in expediting polysulfide conversion and hence essentially restricting the “shuttle effect” in Li–S systems. Nevertheless, seldom efforts have been devoted to probing the dual‐directional polysulfide electrocatalysis to date. Herein, a CoFe alloy decorated mesoporous carbon sphere (CoFe‐MCS) serving as a promising mediator for Li–S batteries is reported. Such bimetallic alloying boosts dual‐directional electrocatalytic activity toward effective polysulfide conversion throughout detailed electroanalytic characterization, theoretical calculation, and operando instrumental probing. Accordingly, the S@CoFe‐MCS cathode harvests a stable cycling with a low capacity decay rate of 0.062% per cycle over 500 cycles at 2.0 C. More encouragingly, benefiting from the optimized redox kinetics and delicate grid architecture, printable S@CoFe‐MCS cathode achieves an excellent rate performance at a sulfur loading of 4.0 mg cm−2 and advanced areal capacity of 6.0 mAh cm−2 at 7.7 mg cm−2. This work explores non‐precious metal alloy electrocatalysts in printable cathodes toward dual‐directional polysulfide conversion, holding great potential in the pursuit of Li–S commercialization.

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Chemisorption and electrocatalytic effect from CoxSny alloy for high performance lithium sulfur batteries

Cited by 80 publications

References 52 publications

Anchoring Polysulfides and Accelerating Redox Reaction Enabled by Fe‐Based Compounds in Lithium–Sulfur Batteries

Anchoring Polysulfides and Accelerating Redox Reaction Enabled by Fe‐Based Compounds in Lithium–Sulfur Batteries

Strategies toward High‐Loading Lithium–Sulfur Battery

Boosting Dual‐Directional Polysulfide Electrocatalysis via Bimetallic Alloying for Printable Li–S Batteries

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