采用不同的实验方法制备了M oS2纳米管,并对其结构、形貌及储氢性能进行了研究.实验表明,经KOH处理的M oS2纳米管在25℃及3 M Pa时,气态储氢容量达到1.2 w t%,在25℃及50 mA.-g 1的放电电流密度下,阳大的电化学储氢容量可达262 mA h.-g...采用不同的实验方法制备了M oS2纳米管,并对其结构、形貌及储氢性能进行了研究.实验表明,经KOH处理的M oS2纳米管在25℃及3 M Pa时,气态储氢容量达到1.2 w t%,在25℃及50 mA.-g 1的放电电流密度下,阳大的电化学储氢容量可达262 mA h.-g 1(相当于1.0 w t%的储氢量);而T iS2纳米管在25℃及4M Pa时气态储氢容量达到2.5 w t%.因此,M oS2和T iS2化合物纳米管具有潜在的储氢应用前景.展开更多
The electronic and optical properties of TiS2 are studied of density functional theory. A linearized and augmented by using an ab-initio calculation within the frame plane wave basis set with the generalized gradient ...The electronic and optical properties of TiS2 are studied of density functional theory. A linearized and augmented by using an ab-initio calculation within the frame plane wave basis set with the generalized gradient approximation as proposed by Perdew et al. is used for the energy exchange-correlation determination. The results show a metallic character of TiS2, and the plots of total and partial densities of states of TiS2 show the metallic character of the bonds and a strong hybridization between the states d of Ti and p of S below the Fermi energy. The optical properties of the material such as real and imaginary parts of dielectric constant （ε（w） = ε1（w） ＋ iε2（w））, refractive index n（w）, optical reflectivity R（w）, for E / /x and E / /z are performed for the energy range of 0-.14 eV.展开更多
Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) un...Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_(1)2_(1)2_(1).Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.展开更多
Alloying-type metal sulfides with high sodiation activity and theoretical capacity are promising anode materials for high energy density sodium ion batteries.However,the large volume change and the migratory and aggre...Alloying-type metal sulfides with high sodiation activity and theoretical capacity are promising anode materials for high energy density sodium ion batteries.However,the large volume change and the migratory and aggregation behavior of metal atoms will cause severe capacity decay during the charge/discharge process.Herein,a robust and conductive TiS_(2)framework is integrated with a high-capacity SbS layer to construct a single phase(SbS)_(1.15)TiS_(2)superlattice for both high-capacity and fast Na^(+)storage.The metallic TiS_(2)sublayer with high electron activity acts as a robust and conductive skeleton to buffer the volume expansion caused by conversion and alloying reaction between Na+and SbS sublayer.Hence,high capacity and high rate capability can be synergistically realized in a single phase(SbS)_(1.15)TiS_(2)superlattice.The novel(SbS)_(1.15)TiS_(2)anode has a high charge capacity of 618 mAh g^(-1)at 0.2 C and superior rate performance and cycling stability(205 mAh g^(-1)at 35 C after 2,000 cycles).Furthermore,in situ and ex situ characterizations are applied to get an insight into the multi-step reaction mechanism.The integrity of robust Na-Ti-S skeleton during(dis)charge process can be confirmed.This superlattice construction idea to integrate the Na^(+)-active unit and electron-active unit would provide a new avenue for exploring high-performance anode materials for advanced sodium-ion batteries.展开更多
Aqueous rechargeable zinc-ion batteries(ARZIBs)have a bright future for energy storage due to their high energy density and safety.However,for traditional ARZIBs,cathode materials always suffer from the limited space ...Aqueous rechargeable zinc-ion batteries(ARZIBs)have a bright future for energy storage due to their high energy density and safety.However,for traditional ARZIBs,cathode materials always suffer from the limited space for large-sized zinc ions storage and transport,leading to low Coulombic efficiency and inferior cycling performance.To build a reliable host with large tunnel,1-butyl-1-methylpyrrolidinium ion(PY14^(+))pre-intercalated TiS_(2)(PY14^(+)-TiS_(2))is designed as an alternative intercalation-type electrode.As the insertion organic guest widens the interlayer space of TiS_(2)and buffers the lattice stress generated during the electrochemical cycles,the structural reversibility,cycling stability and kinetics properties of PY14^(+)-TiS_(2) are enhanced greatly.A specific capacity of 130.9 mAh g^(−1) with 84.3%capacity retention over 500 cycles can be achieved at 0.1 A g^(−1).Therefore,this study paves the way for enhancing the aqueous Zn ions storage capability by organic interlayer engineering.展开更多
As an alternative for lithium-ion batteries(LIBs),sodium-ion batteries(SIBs)have lately received tremendous interest due to their abundant reserves as well as low cost.Nevertheless,the lack of suitable anode materials...As an alternative for lithium-ion batteries(LIBs),sodium-ion batteries(SIBs)have lately received tremendous interest due to their abundant reserves as well as low cost.Nevertheless,the lack of suitable anode materials severely hinders the application of sodium-ion batteries.TiS_(2)is elected as a representative material owing to its unique layered structure.But it always suffers from capacity fade due to poor electrochemical kinetics and structural stability.In this work,we fabricate a pre-potassiated TiS_(2)as a host material for sodium storage by an electrochemical pre-potassiation strategy.The intercalation/extraction mechanism,structural changes and reaction kinetics are completely investigated to reveal the outstanding electrochemical property of pre-potassiated TiS_(2)electrode.It turns out that the large interlayer space of pre-potassiated TiS_(2)is conducive to the diffusion of sodium ions,inducing the reduction of entropic barrier for the electrochemical reactions.In addition,the pre-potassiated host structure is still firmly maintained upon repeated cycles.Therefore,the pre-potassiated TiS_(2)presents superior rate capability(165.9 mA h g^(−1) at 1 C and 132.1 mA h g^(−1) at 20 C)and long-term cycling stability(85.3%capacity retention at 5 C after 500 cycles)for SIBs.This research provides an avenue to construct long-life sodium energy storage systems based on pre-potassiated TiS_(2).展开更多
Lithium-sulfur batteries have attracted attention because of their high energy density.However,the "shuttle effect" caused by the dissolving of polysulfide in the electrolyte has greatly hindered the widespr...Lithium-sulfur batteries have attracted attention because of their high energy density.However,the "shuttle effect" caused by the dissolving of polysulfide in the electrolyte has greatly hindered the widespread commercial use of lithiumsulfur batteries.In this paper,a novel two-dimensional TiS2/graphene heterostructure is theoretically designed as the anchoring material for lithium-sulfur batteries to suppress the shuttle effect.This heterostructure formed by the stacking of graphene and TiS2 monolayer is the van der Waals type,which retains the intrinsic metallic electronic structure of graphene and TiS2 monolayer.Graphene improves the electronic conductivity of the sulfur cathode,and the transferred electrons from graphene enhance the polarity of the TiS2 monolayer.Simulations of the polysulfide adsorption show that the TiS2/graphene hetero structure can maintain good metallic properties and the appropriate adsorption energies of 0.98-3.72 eV,which can effectively anchor polysulfides.Charge transfer analysis suggests that further enhancement of polarity is beneficial to reduce the high proportion of van der Waals(vdW) force in the adsorption energy,thereby further enhancing the anchoring ability.Low Li2 S decomposition barrier and Li-ion migration barrier imply that the heterostructure has the ability to catalyze fast electrochemical kinetic processes.Therefore,TiS2/graphene heterostructure could be an important candidate for ideal anchoring materials of lithium-sulfur batteries.展开更多
文摘采用不同的实验方法制备了M oS2纳米管,并对其结构、形貌及储氢性能进行了研究.实验表明,经KOH处理的M oS2纳米管在25℃及3 M Pa时,气态储氢容量达到1.2 w t%,在25℃及50 mA.-g 1的放电电流密度下,阳大的电化学储氢容量可达262 mA h.-g 1(相当于1.0 w t%的储氢量);而T iS2纳米管在25℃及4M Pa时气态储氢容量达到2.5 w t%.因此,M oS2和T iS2化合物纳米管具有潜在的储氢应用前景.
文摘The electronic and optical properties of TiS2 are studied of density functional theory. A linearized and augmented by using an ab-initio calculation within the frame plane wave basis set with the generalized gradient approximation as proposed by Perdew et al. is used for the energy exchange-correlation determination. The results show a metallic character of TiS2, and the plots of total and partial densities of states of TiS2 show the metallic character of the bonds and a strong hybridization between the states d of Ti and p of S below the Fermi energy. The optical properties of the material such as real and imaginary parts of dielectric constant （ε（w） = ε1（w） ＋ iε2（w））, refractive index n（w）, optical reflectivity R（w）, for E / /x and E / /z are performed for the energy range of 0-.14 eV.
基金supported by the National Natural Science Foundation of China (Grant No. 12304072)Program for Science and Technology Innovation Team in Zhejiang (Grant No. 2021R01004)+1 种基金Natural Science Foundation of Ningbo(Grant No. 2021J121)supported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
文摘Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_(1)2_(1)2_(1).Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.
基金supported by the National Key Research and Development Program of China(2019YFA0210600)the National Natural Science Foundation of China(51922103 and 51972326)。
文摘Alloying-type metal sulfides with high sodiation activity and theoretical capacity are promising anode materials for high energy density sodium ion batteries.However,the large volume change and the migratory and aggregation behavior of metal atoms will cause severe capacity decay during the charge/discharge process.Herein,a robust and conductive TiS_(2)framework is integrated with a high-capacity SbS layer to construct a single phase(SbS)_(1.15)TiS_(2)superlattice for both high-capacity and fast Na^(+)storage.The metallic TiS_(2)sublayer with high electron activity acts as a robust and conductive skeleton to buffer the volume expansion caused by conversion and alloying reaction between Na+and SbS sublayer.Hence,high capacity and high rate capability can be synergistically realized in a single phase(SbS)_(1.15)TiS_(2)superlattice.The novel(SbS)_(1.15)TiS_(2)anode has a high charge capacity of 618 mAh g^(-1)at 0.2 C and superior rate performance and cycling stability(205 mAh g^(-1)at 35 C after 2,000 cycles).Furthermore,in situ and ex situ characterizations are applied to get an insight into the multi-step reaction mechanism.The integrity of robust Na-Ti-S skeleton during(dis)charge process can be confirmed.This superlattice construction idea to integrate the Na^(+)-active unit and electron-active unit would provide a new avenue for exploring high-performance anode materials for advanced sodium-ion batteries.
基金supported by the NSAF joint Fund(No.U1830106)the National Natural Science Foundation of China(No.U1632114).
文摘Aqueous rechargeable zinc-ion batteries(ARZIBs)have a bright future for energy storage due to their high energy density and safety.However,for traditional ARZIBs,cathode materials always suffer from the limited space for large-sized zinc ions storage and transport,leading to low Coulombic efficiency and inferior cycling performance.To build a reliable host with large tunnel,1-butyl-1-methylpyrrolidinium ion(PY14^(+))pre-intercalated TiS_(2)(PY14^(+)-TiS_(2))is designed as an alternative intercalation-type electrode.As the insertion organic guest widens the interlayer space of TiS_(2)and buffers the lattice stress generated during the electrochemical cycles,the structural reversibility,cycling stability and kinetics properties of PY14^(+)-TiS_(2) are enhanced greatly.A specific capacity of 130.9 mAh g^(−1) with 84.3%capacity retention over 500 cycles can be achieved at 0.1 A g^(−1).Therefore,this study paves the way for enhancing the aqueous Zn ions storage capability by organic interlayer engineering.
基金sponsored by NSAF joint Fund(U1830106)Science and Technology Innovation 2025 Major Program of Ningbo(2018B10061)+1 种基金National Natural Science Foundation of China(U1632114,51901205)K.C.Wong Magna Fund in Ningbo University。
文摘As an alternative for lithium-ion batteries(LIBs),sodium-ion batteries(SIBs)have lately received tremendous interest due to their abundant reserves as well as low cost.Nevertheless,the lack of suitable anode materials severely hinders the application of sodium-ion batteries.TiS_(2)is elected as a representative material owing to its unique layered structure.But it always suffers from capacity fade due to poor electrochemical kinetics and structural stability.In this work,we fabricate a pre-potassiated TiS_(2)as a host material for sodium storage by an electrochemical pre-potassiation strategy.The intercalation/extraction mechanism,structural changes and reaction kinetics are completely investigated to reveal the outstanding electrochemical property of pre-potassiated TiS_(2)electrode.It turns out that the large interlayer space of pre-potassiated TiS_(2)is conducive to the diffusion of sodium ions,inducing the reduction of entropic barrier for the electrochemical reactions.In addition,the pre-potassiated host structure is still firmly maintained upon repeated cycles.Therefore,the pre-potassiated TiS_(2)presents superior rate capability(165.9 mA h g^(−1) at 1 C and 132.1 mA h g^(−1) at 20 C)and long-term cycling stability(85.3%capacity retention at 5 C after 500 cycles)for SIBs.This research provides an avenue to construct long-life sodium energy storage systems based on pre-potassiated TiS_(2).
基金Project supported by the National Natural Science Foundation of China(Grant Nos.62104168,11604235,andU1510132)the Beijing Institute of Technology Research Fund Program for Young Scholars+2 种基金the Natural Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi,China(Grant No.2019L0309)the Natural Science Foundation of Shanxi Province,China(Grant Nos.201901D111125 and 20210302123201)the Shanxi Scholarship Council of China。
文摘Lithium-sulfur batteries have attracted attention because of their high energy density.However,the "shuttle effect" caused by the dissolving of polysulfide in the electrolyte has greatly hindered the widespread commercial use of lithiumsulfur batteries.In this paper,a novel two-dimensional TiS2/graphene heterostructure is theoretically designed as the anchoring material for lithium-sulfur batteries to suppress the shuttle effect.This heterostructure formed by the stacking of graphene and TiS2 monolayer is the van der Waals type,which retains the intrinsic metallic electronic structure of graphene and TiS2 monolayer.Graphene improves the electronic conductivity of the sulfur cathode,and the transferred electrons from graphene enhance the polarity of the TiS2 monolayer.Simulations of the polysulfide adsorption show that the TiS2/graphene hetero structure can maintain good metallic properties and the appropriate adsorption energies of 0.98-3.72 eV,which can effectively anchor polysulfides.Charge transfer analysis suggests that further enhancement of polarity is beneficial to reduce the high proportion of van der Waals(vdW) force in the adsorption energy,thereby further enhancing the anchoring ability.Low Li2 S decomposition barrier and Li-ion migration barrier imply that the heterostructure has the ability to catalyze fast electrochemical kinetic processes.Therefore,TiS2/graphene heterostructure could be an important candidate for ideal anchoring materials of lithium-sulfur batteries.
