A new Fe3C-N-doped reduced graphene oxide(Fe3C-N-rGO)prepared by a facile method is used as a separator for high performance lithium-sulfur(Li-S)batteries.The Fe3C-N-rGO is coated on the surface of commercial polyprop...A new Fe3C-N-doped reduced graphene oxide(Fe3C-N-rGO)prepared by a facile method is used as a separator for high performance lithium-sulfur(Li-S)batteries.The Fe3C-N-rGO is coated on the surface of commercial polypropylene separator(Celgard 2400)close to the sulfur cathode.The special nanotubes are in-situ catalyzed by Fe3C nanoparticles.They could entrap lithium polysulfides(Li PSs)to restrain the shuttle effect and reduce the loss of active material.The battery with the modified separator and sulfur cathode shows an excellent cycle performance.It has a high rate performance,580.5 mAh/g at the high current rate of 4 C relative to 1075 mAh/g at 0.1 C.It also has an initial discharge capacity of 774.8 m Ah/g measured at 0.5 C and remains 721.8 mAh/g after 100 cycles with a high capacity retention of 93.2%.The outstanding performances are notable in recently reports with modified separator.展开更多
Lithium-sulfur batteries(LSBs)are promising alternative energy storage devices to the commercial lithium-ion batteries.However,the LSBs have several limitations including the low electronic conductivity of sulfur(5...Lithium-sulfur batteries(LSBs)are promising alternative energy storage devices to the commercial lithium-ion batteries.However,the LSBs have several limitations including the low electronic conductivity of sulfur(5×10^-30S cm^-1),associated lithium polysulfides(PSs),and their migration from the cathode to the anode.In this study,a separator coated with a Ketjen black(KB)/Nafion composite was used in an LSB with a sulfur loading up to 7.88 mg cm^-2to mitigate the PS migration.A minimum specific capacity(Cs)loss of 0.06%was obtained at 0.2 C-rate at a high sulfur loading of 4.39 mg cm^-2.Furthermore,an initial areal capacity up to 6.70 mAh cm^-2 was obtained at a sulfur loading of 7.88 mg cm^-2.The low Cs loss and high areal capacity associated with the high sulfur loading are attributed to the large surface area of the KB and sulfonate group(SO3^-)of Nafion,respectively,which could physically and chemically trap the PSs.展开更多
The practical application of lithium–sulfur(Li–S)batteries is limited by the easy dissolution of polysulfides in the electrolyte,resulting in the lithium polysulfide(LPS)shuttle effect.Several two-dimensional(2D)mat...The practical application of lithium–sulfur(Li–S)batteries is limited by the easy dissolution of polysulfides in the electrolyte,resulting in the lithium polysulfide(LPS)shuttle effect.Several two-dimensional(2D)materials with abundant active binding sites and high surface-to-volume ratios have been developed to prepare functional separators that suppress the diffusion of polysulfides.However,the influence of modified layer thickness on Li+transport has not been considered.Herein,we synthesized individual and multilayered 2D Ti3C2Tx MXene nanosheets and used them to fabricate a series of Ti3C2Tx-PP modified separators.The separators had mass loadings ranging from 0.16 to 0.016 mg cm-2,which is the lowest value reported for 2D materials to the best of our knowledge.The corresponding reductions in thickness ranged from 1.2μm to 100 nm.LPS shuttling was effectively suppressed,even at the lowest mass loading of 0.016 mg cm-2.Suppression was due to the strong interaction between LPS intermediates and Ti atoms and hydroxyl functional groups on the separator surface.The lithium-ion diffusion coefficient increased with the reduction of Ti3C2Tx layers on the separator.Superior cycling stability and rate performance were attained when the separator with a Ti3C2Tx-PP mass loading of 0.016 mg cm-2 was incorporated into a Li–S battery.Carbon nanotubes(CNTs)were introduced into the separators to further improve the electrical and Li+ionic conductivity in the cross-plane direction of the 2D Ti3C2Txlayers.With the ultralightweight Ti3C2Tx/CNTs modified PP separator,the cell maintained a capacity of 640 m Ah g-1after 200cycles at 1C with a capacity decay of only 0.079%per cycle.展开更多
The notorious shuttle effect has long been obstructing lithium-sulfur(Li-S) batteries from yielding the expected high energy density and long lifespan.Herein,we develop a multifunctional polysulfide barrier reinforced...The notorious shuttle effect has long been obstructing lithium-sulfur(Li-S) batteries from yielding the expected high energy density and long lifespan.Herein,we develop a multifunctional polysulfide barrier reinforced by the graphitic carbon nitride/carbon nanotube(g-C_3 N_4/CNT) composite toward inhibited shuttling behavior and improved battery performance.The obtained g-C_3 N_4 delivers a unique spongelike architecture with massive ion transfer pathways and fully exposed active interfaces,while the abundant C-N heteroatomic structures impose strong chemical immobilization toward lithium polysulfides.Combined with the highly conductive agent,the g-C_3 N_4/CNT reinforced separator is endowed with great capability of confining and reutilizing the active sulfur within the cathode,thus contributing to an efficient and stable sulfur electrochemistry.Benefiting from these synergistic attributes,Li-S cells based on g-C_3 N_4/CNT separator exhibit an excellent cyclability with a minimum decay rate of 0.03% per cycle over 500 cycles and decent rate capability up to 2 C.Moreover,a high areal capacity of 7.69 mAh cm^(-2)can be achieved under a raised sulfur loading up to 10.1 mg cm^(-2).demonstrating a facile and efficient pathway toward superior Li-S batteries.展开更多
Lithium-sulfur(Li-S)batteries are receiving increasing attention as one of the potential next-generation batteries,owing to their high energy densities and low cost.However,practical Li-S batteries with high energy de...Lithium-sulfur(Li-S)batteries are receiving increasing attention as one of the potential next-generation batteries,owing to their high energy densities and low cost.However,practical Li-S batteries with high energy densities are extremely hindered by the sulfur loss,low Coulombic efficiency,and short cycling life originating from the polysulfide(LiPS)shuttle.In this study,two-dimensional(2D)ZnCo_(2)O_(4) microsheets fabricated by a facile hydrothermal process are employed to modify the separator,for improving the electrochemical performances of Li-S cells.The resulting 2D Zn Co_(2)O_(4)-coated separator features a coating thickness of approximately 10 lm,high ionic conductivity of 1.8 m S/cm,and low mass loading of 0.2 mg/cm^(2).This 2D ZnCo_(2)O_(4)-coated separator effectively inhibits Li PS shuttle by a strong chemical interaction with Li PS as well as promotes the redox kinetics by Zn CO2O4-coated layers,as determined by X-ray photoelectron spectroscopy analysis,self-discharge,time-dependent permeation test,Li symmetric cell test,and Li2S nucleation analyses.Consequently,the Li-S batteries based on the 2D Zn Co_(2)O_(4)-coated separator exhibit a high initial discharge capacity of 1292.2 m Ah/g at 0.1 C.Moreover,they exhibit excellent long cycle stability at 1 and 2 C with capacity retention of 84%and 86%even after800 cycles,corresponding to a capacity fading rate of 0.020%and 0.016%per cycle,respectively.Effectively,these Li-S cells with a high sulfur loading at 5.3 mg/cm^(2) and low electrolyte concentration of 9 l L/mg deliver a high discharge capacity of 4.99 m Ah/cm^(2) after 200 cycles at 0.1 C.展开更多
Structure manipulation of photocatalysts at an atomic scale is a promising way to improve its photocatalytic performance.Herein,we realize the anchoring of single Ni atoms on the ZnIn_(2)S_(4) nanosheets with rich sul...Structure manipulation of photocatalysts at an atomic scale is a promising way to improve its photocatalytic performance.Herein,we realize the anchoring of single Ni atoms on the ZnIn_(2)S_(4) nanosheets with rich sulfur vacancies.Experimental results demonstrate that single Ni atoms induce the formation of NiO-M(Zn/In) atomic interface,which can efficiently promote the carriers separation and prolong the carrier life time.In addition,in situ electron spin resonance spectroscopy(ESR) confirms that the single Ni atoms act as an electron trapping center for protons reduction.As a result,the single Ni atoms decorated ZnIn_(2)S_(4) nanosheets with rich sulfur vacancies(Ni/ZnIn_(2)S_(4)-RVs) shows a hydrogen evolution rate up to 89.4 μmol h^(-1), almost 5.7 and 2.3 times higher compared to that of ZnIn_(2)S_(4) nanosheets with poor sulfur vacancies and rich sulfur vacancies(denoted as ZnIn_(2)S_(4)-PVs and ZnIn_(2)S_(4)-RVs).This work opens up a new perspective manipulating the single-atom cocatalyst and sulfur vacancy on sulfide supports for improving photocatalytic hydrogen evolution.展开更多
基金supported by the National Natural Science Foundation of China(Grant no.51672075,21271069,51772092,51704106)Science and Technology Program of Hunan Province(Grant no.2015JC3049)
文摘A new Fe3C-N-doped reduced graphene oxide(Fe3C-N-rGO)prepared by a facile method is used as a separator for high performance lithium-sulfur(Li-S)batteries.The Fe3C-N-rGO is coated on the surface of commercial polypropylene separator(Celgard 2400)close to the sulfur cathode.The special nanotubes are in-situ catalyzed by Fe3C nanoparticles.They could entrap lithium polysulfides(Li PSs)to restrain the shuttle effect and reduce the loss of active material.The battery with the modified separator and sulfur cathode shows an excellent cycle performance.It has a high rate performance,580.5 mAh/g at the high current rate of 4 C relative to 1075 mAh/g at 0.1 C.It also has an initial discharge capacity of 774.8 m Ah/g measured at 0.5 C and remains 721.8 mAh/g after 100 cycles with a high capacity retention of 93.2%.The outstanding performances are notable in recently reports with modified separator.
基金the Australian Government and University of Queensland for the research training program scholarship and research facilities used in this study.
文摘Lithium-sulfur batteries(LSBs)are promising alternative energy storage devices to the commercial lithium-ion batteries.However,the LSBs have several limitations including the low electronic conductivity of sulfur(5×10^-30S cm^-1),associated lithium polysulfides(PSs),and their migration from the cathode to the anode.In this study,a separator coated with a Ketjen black(KB)/Nafion composite was used in an LSB with a sulfur loading up to 7.88 mg cm^-2to mitigate the PS migration.A minimum specific capacity(Cs)loss of 0.06%was obtained at 0.2 C-rate at a high sulfur loading of 4.39 mg cm^-2.Furthermore,an initial areal capacity up to 6.70 mAh cm^-2 was obtained at a sulfur loading of 7.88 mg cm^-2.The low Cs loss and high areal capacity associated with the high sulfur loading are attributed to the large surface area of the KB and sulfonate group(SO3^-)of Nafion,respectively,which could physically and chemically trap the PSs.
基金financially supported by the National Natural Science Foundation of China(21706292)support from the Hunan Provincial Science and Technology Plan Project,China(No.2017TP1001).
文摘The practical application of lithium–sulfur(Li–S)batteries is limited by the easy dissolution of polysulfides in the electrolyte,resulting in the lithium polysulfide(LPS)shuttle effect.Several two-dimensional(2D)materials with abundant active binding sites and high surface-to-volume ratios have been developed to prepare functional separators that suppress the diffusion of polysulfides.However,the influence of modified layer thickness on Li+transport has not been considered.Herein,we synthesized individual and multilayered 2D Ti3C2Tx MXene nanosheets and used them to fabricate a series of Ti3C2Tx-PP modified separators.The separators had mass loadings ranging from 0.16 to 0.016 mg cm-2,which is the lowest value reported for 2D materials to the best of our knowledge.The corresponding reductions in thickness ranged from 1.2μm to 100 nm.LPS shuttling was effectively suppressed,even at the lowest mass loading of 0.016 mg cm-2.Suppression was due to the strong interaction between LPS intermediates and Ti atoms and hydroxyl functional groups on the separator surface.The lithium-ion diffusion coefficient increased with the reduction of Ti3C2Tx layers on the separator.Superior cycling stability and rate performance were attained when the separator with a Ti3C2Tx-PP mass loading of 0.016 mg cm-2 was incorporated into a Li–S battery.Carbon nanotubes(CNTs)were introduced into the separators to further improve the electrical and Li+ionic conductivity in the cross-plane direction of the 2D Ti3C2Txlayers.With the ultralightweight Ti3C2Tx/CNTs modified PP separator,the cell maintained a capacity of 640 m Ah g-1after 200cycles at 1C with a capacity decay of only 0.079%per cycle.
基金supported by the National Natural Science Foundation of China (Nos. 21978110 and 51772126)the Natural Science Foundation of Beijing (No. L182062)+8 种基金the Organization Department of Beijing Talents Project (2018000021223ZK21)the Yue Qi Young Scholar Project of China University of Mining & Technology (Beijing) (No. 2017QN17)the Fundamental Research Funds for the Central Universities (No. 2014QJ02)the Jilin Province Science and Technology Department Program (Nos. 20200201187JC, 20190201309JC, and 20190101009JH)the ‘‘13th five-year” Science and Technology Project of Jilin Provincial Education Department (No. JJKH20200407KJ)the Jilin Province Development and Reform Commission Program (Nos. 2020C026-3 and 2019C042-1)the Jilin Province Fund for Talent Development Program (No. [2019] 874)the supports from Natural Sciences and Engineering Research Council of Canada (NSERC), the University of Waterloothe Waterloo Institute for Nanotechnology。
文摘The notorious shuttle effect has long been obstructing lithium-sulfur(Li-S) batteries from yielding the expected high energy density and long lifespan.Herein,we develop a multifunctional polysulfide barrier reinforced by the graphitic carbon nitride/carbon nanotube(g-C_3 N_4/CNT) composite toward inhibited shuttling behavior and improved battery performance.The obtained g-C_3 N_4 delivers a unique spongelike architecture with massive ion transfer pathways and fully exposed active interfaces,while the abundant C-N heteroatomic structures impose strong chemical immobilization toward lithium polysulfides.Combined with the highly conductive agent,the g-C_3 N_4/CNT reinforced separator is endowed with great capability of confining and reutilizing the active sulfur within the cathode,thus contributing to an efficient and stable sulfur electrochemistry.Benefiting from these synergistic attributes,Li-S cells based on g-C_3 N_4/CNT separator exhibit an excellent cyclability with a minimum decay rate of 0.03% per cycle over 500 cycles and decent rate capability up to 2 C.Moreover,a high areal capacity of 7.69 mAh cm^(-2)can be achieved under a raised sulfur loading up to 10.1 mg cm^(-2).demonstrating a facile and efficient pathway toward superior Li-S batteries.
基金supported by a grant from R&D Program of the Korea Railroad Research Institute,Republic of Korea。
文摘Lithium-sulfur(Li-S)batteries are receiving increasing attention as one of the potential next-generation batteries,owing to their high energy densities and low cost.However,practical Li-S batteries with high energy densities are extremely hindered by the sulfur loss,low Coulombic efficiency,and short cycling life originating from the polysulfide(LiPS)shuttle.In this study,two-dimensional(2D)ZnCo_(2)O_(4) microsheets fabricated by a facile hydrothermal process are employed to modify the separator,for improving the electrochemical performances of Li-S cells.The resulting 2D Zn Co_(2)O_(4)-coated separator features a coating thickness of approximately 10 lm,high ionic conductivity of 1.8 m S/cm,and low mass loading of 0.2 mg/cm^(2).This 2D ZnCo_(2)O_(4)-coated separator effectively inhibits Li PS shuttle by a strong chemical interaction with Li PS as well as promotes the redox kinetics by Zn CO2O4-coated layers,as determined by X-ray photoelectron spectroscopy analysis,self-discharge,time-dependent permeation test,Li symmetric cell test,and Li2S nucleation analyses.Consequently,the Li-S batteries based on the 2D Zn Co_(2)O_(4)-coated separator exhibit a high initial discharge capacity of 1292.2 m Ah/g at 0.1 C.Moreover,they exhibit excellent long cycle stability at 1 and 2 C with capacity retention of 84%and 86%even after800 cycles,corresponding to a capacity fading rate of 0.020%and 0.016%per cycle,respectively.Effectively,these Li-S cells with a high sulfur loading at 5.3 mg/cm^(2) and low electrolyte concentration of 9 l L/mg deliver a high discharge capacity of 4.99 m Ah/cm^(2) after 200 cycles at 0.1 C.
基金the support of the National Natural Science Foundation of China(51702087,21673066)the Project funded by the China Postdoctoral Science Foundation(2019M652516)。
文摘Structure manipulation of photocatalysts at an atomic scale is a promising way to improve its photocatalytic performance.Herein,we realize the anchoring of single Ni atoms on the ZnIn_(2)S_(4) nanosheets with rich sulfur vacancies.Experimental results demonstrate that single Ni atoms induce the formation of NiO-M(Zn/In) atomic interface,which can efficiently promote the carriers separation and prolong the carrier life time.In addition,in situ electron spin resonance spectroscopy(ESR) confirms that the single Ni atoms act as an electron trapping center for protons reduction.As a result,the single Ni atoms decorated ZnIn_(2)S_(4) nanosheets with rich sulfur vacancies(Ni/ZnIn_(2)S_(4)-RVs) shows a hydrogen evolution rate up to 89.4 μmol h^(-1), almost 5.7 and 2.3 times higher compared to that of ZnIn_(2)S_(4) nanosheets with poor sulfur vacancies and rich sulfur vacancies(denoted as ZnIn_(2)S_(4)-PVs and ZnIn_(2)S_(4)-RVs).This work opens up a new perspective manipulating the single-atom cocatalyst and sulfur vacancy on sulfide supports for improving photocatalytic hydrogen evolution.
