Adjusting the interfacial transport efficiency of photogenerated electrons and the free energy of hydrogen adsorption through interface engineering is an effective means of improving the photocatalytic activity of sem...Adjusting the interfacial transport efficiency of photogenerated electrons and the free energy of hydrogen adsorption through interface engineering is an effective means of improving the photocatalytic activity of semiconductor photocatalysts.Herein,hollow ZnS/NiS nanocages with ohmic contacts containing Zn vacancy(V_(Zn)-ZnS/NiS)are synthesized using ZIF-8 as templates.An internal electric field is constructed by Fermi level flattening to form ohmic contacts,which increase donor density and accelerate electron transport at the V_(Zn)-ZnS/NiS interface.The experimental and DFT results show that the tight interface and V_(Zn) can rearrange electrons,resulting in a higher charge density at the interface,and optimizing the Gibbs free energy of hydrogen adsorption.The optimal hydrogen production activity of V_(Zn)-ZnS/NiS is 10,636 μmol h^(-1) g^(-1),which is 31.9 times that of V_(Zn)-ZnS.This study provides an idea for constructing sulfide heterojunctions with ohmic contacts and defects to achieve efficient photocatalytic hydrogen production.展开更多
Aqueous zinc ion batteries are regarded as one of the most promising candidates for large-scale energy stor-age due to their high safety,cost-effectiveness,and environ-mental friendliness.However,uncontrolled zinc den...Aqueous zinc ion batteries are regarded as one of the most promising candidates for large-scale energy stor-age due to their high safety,cost-effectiveness,and environ-mental friendliness.However,uncontrolled zinc dendrite growth and side reactions of the zinc anode decrease the sta-bility of Zn batteries.We report the synthesis of an air-oxid-ized carbon nanotube(O-CNT)film by chemical vapor de-position followed by heat treatment in air which is used as a protective layer on the Zn foil to suppress zinc dendrite growth.The increase in the hydrophilicity of the O-CNT film caused by air oxidation facilitates zinc deposition between the film and the anode instead of deposition on the film surface.The porous structure of the O-CNT film homogenizes the Zn^(2+)ion flux and the electric field on the surface of the Zn foil,leading to the uniform deposition of Zn.As a result,a O-CNT@Zn symmetric cell has a much better cycling stability with a life of more than 3000 h at 1 mA cm^(−2) with a capacity of 1 mAh cm^(−2),and values of more than 2000 h and 1 mAh cm^(−2) at 5 mA cm^(−2).In addition,a O-CNT@Zn||Mn^(2+)inserted hydrated vanadium pentoxide(MnVOH)full cell has a better rate per-formance than a Zn||MnVOH cell,achieving a high discharge capacity of 194 mAh g^(−1) at a high current density of 8 A g^(−1).In a long-term cycling test,the O-CNT@Zn||MnVOH full cell has a capacity retention of 58.8%after 2000 cycles at a current density of 5 A·g^(−1).展开更多
Rechargeable aqueous zinc-metal batteries (AZMBs) are promising candidates for large-scale energy storage systems due to their low cost and high safety.However,their performance and sustainability are significantly hi...Rechargeable aqueous zinc-metal batteries (AZMBs) are promising candidates for large-scale energy storage systems due to their low cost and high safety.However,their performance and sustainability are significantly hindered by the sluggish desolvation kinetics at the electrode/electrolyte interface and the corresponding hydrogen evolution reaction where active water molecules tightly participate in the Zn(H_(2)O)_(6)^(2+)solvation shell.Herein,learnt from self-generated solid electrolyte interphase (SEI) in anodes,the dielectric but ion-conductive zinc niobate nanoparticles artificial layer is constructed on metallic Zn surface (ZNB@Zn),acting as a rapid desolvation promotor.The zincophilic and dielectric-conductive properties of ZNB layer accelerate interfacial desolvation/diffusion and suppress surface corrosion or dendrite formation,achieving uniform Zn plating/stripping behavior,as confirmed by electronic/optical microscopies and interface spectroscopical measurements together with theoretical calculations.Consequently,the as-prepared ZNB@Zn electrode exhibits excellent cycling stability of over 2000 h and robust reversibility (99.54%) even under high current density and depth of discharge conditions.Meanwhile,the assembled ZNB@Zn-based full cell displays high capacity-retention rate of 80.21%after 3000 cycles at 5 A g^(-1)and outstanding rate performance up to 10 A g^(-1).The large-areal pouch cell is stabilized for hundreds of cycles,highlighting the bright prospects of the dielectric but ion-conductive layer in further application of AZMBs.展开更多
Flexible Zn-based batteries have attracted increasing research interest as essential components of wearable energy storage devices.However,the advancement of flexible aqueous Zn-based batteries based on Co-Ni layered ...Flexible Zn-based batteries have attracted increasing research interest as essential components of wearable energy storage devices.However,the advancement of flexible aqueous Zn-based batteries based on Co-Ni layered double hydroxide (CoNi-LDH) as the cathode material is hampered by their poor cycling stability and the corrosiveness of alkaline electrolytes.Herein,CoNi-LDH nanosheets enriched with H vacancies (CoNi-LDH(v)) were constructed on a flexible carbon cloth (CC) substrate via electrochemical deposition and activation.The Zn-based battery comprising CoNi-LDH(v)@CC as the cathode exhibited highly reversible conversion reactions and stable operation in 3 M ZnSO4electrolyte (pH=4).The battery delivered an excellent specific capacity (225 mA h g^(-1),0.26 mA h cm^(-2)),acceptable cycling stability(53.9%,900 cycles),and high discharging voltage.The abundant H vacancies served as active sites for the reversible intercalation of Zn^(2+)and the extravasation of NO_(3)-generated channels and space for Zn^(2+)transport and storage,together enabling an excellent Zn^(2+)storage capacity.Furthermore,a sandwich-structured solid-state CoNi-LDH(v)@CC//Zn@CC battery was fabricated and was found to exhibit a noteworthy electrochemical performance and mechanical durability.As a proof of concept,the unencapsulated battery powered a digital watch under various deformation conditions and operated stably for 80 h.Additionally,the flexible battery displayed outstanding customizability,maintaining an open-circuit voltage of 1.42 V even after being cut twice.The proposed engineering strategy contributes to the realization of textiles with truly wearable energy-storage devices.展开更多
ZnS ∶Cu nanoparticles were prepared by using microemulsion method at room temperature. The size of the particles is 2-8 nm by transmission electron microscopy (TEM) and dynamic light scattering (DLS) technique. X-ray...ZnS ∶Cu nanoparticles were prepared by using microemulsion method at room temperature. The size of the particles is 2-8 nm by transmission electron microscopy (TEM) and dynamic light scattering (DLS) technique. X-ray diffraction analysis shows that the particles are cubic crystal structure, the same structure as the bulk ZnS materials. Ultraviolet absorption demonstrates an increased bandgap due to quantum confinement effect. Photoluminescence spectrum shows there is a single green emission band at 482 nm.展开更多
锂硫电池由于其高能量密度、低成本效益被认为是最有前途的下一代电池体系之一.然而多硫化物的穿梭效应大幅降低了锂硫电池的循环稳定性和寿命,严重阻碍其实际应用.无机金属化合物材料改性的隔膜不仅能抑制多硫化锂(LiPS)的穿梭效应,其...锂硫电池由于其高能量密度、低成本效益被认为是最有前途的下一代电池体系之一.然而多硫化物的穿梭效应大幅降低了锂硫电池的循环稳定性和寿命,严重阻碍其实际应用.无机金属化合物材料改性的隔膜不仅能抑制多硫化锂(LiPS)的穿梭效应,其部分特殊的晶面还能加速多硫化物的氧化还原反应动力学.本文在罗盘状ZnS表面原位生长球状的MoO_(2),制备MoO_(2)/ZnS复合材料.MoO_(2)对多硫化物有着较强的吸附作用,ZnS有着良好的电导率,两者的复合可加速电子传导效率和氧化还原速率.以所制备的MoO_(2)/ZnS作为隔膜改性材料,锂硫电池在5 C的大电流密度下,经过1000次循环后仍可以保持690 mAh g^(-1)的放电比容量,平均每圈的容量衰减率仅为0.014%,表现出优异的循环性能和倍率性能.展开更多
基金financially supported by the Natural National Science Foundation of China(22178084)the Natural Science Foundation for Distinguished Young Scholars of Hebei Province(No.B2015208010)+2 种基金Fundamental Research Funds for the Central Universitiesthe Foundation for Innovative Research Groups of the Natural Science Foundation of Hebei Province(No.B2021208005)National Key R&D Program of China(2022YFE0101800).
文摘Adjusting the interfacial transport efficiency of photogenerated electrons and the free energy of hydrogen adsorption through interface engineering is an effective means of improving the photocatalytic activity of semiconductor photocatalysts.Herein,hollow ZnS/NiS nanocages with ohmic contacts containing Zn vacancy(V_(Zn)-ZnS/NiS)are synthesized using ZIF-8 as templates.An internal electric field is constructed by Fermi level flattening to form ohmic contacts,which increase donor density and accelerate electron transport at the V_(Zn)-ZnS/NiS interface.The experimental and DFT results show that the tight interface and V_(Zn) can rearrange electrons,resulting in a higher charge density at the interface,and optimizing the Gibbs free energy of hydrogen adsorption.The optimal hydrogen production activity of V_(Zn)-ZnS/NiS is 10,636 μmol h^(-1) g^(-1),which is 31.9 times that of V_(Zn)-ZnS.This study provides an idea for constructing sulfide heterojunctions with ohmic contacts and defects to achieve efficient photocatalytic hydrogen production.
基金supported by the National Natural Science Foundation of China(22179093 and21905202)。
文摘Aqueous zinc ion batteries are regarded as one of the most promising candidates for large-scale energy stor-age due to their high safety,cost-effectiveness,and environ-mental friendliness.However,uncontrolled zinc dendrite growth and side reactions of the zinc anode decrease the sta-bility of Zn batteries.We report the synthesis of an air-oxid-ized carbon nanotube(O-CNT)film by chemical vapor de-position followed by heat treatment in air which is used as a protective layer on the Zn foil to suppress zinc dendrite growth.The increase in the hydrophilicity of the O-CNT film caused by air oxidation facilitates zinc deposition between the film and the anode instead of deposition on the film surface.The porous structure of the O-CNT film homogenizes the Zn^(2+)ion flux and the electric field on the surface of the Zn foil,leading to the uniform deposition of Zn.As a result,a O-CNT@Zn symmetric cell has a much better cycling stability with a life of more than 3000 h at 1 mA cm^(−2) with a capacity of 1 mAh cm^(−2),and values of more than 2000 h and 1 mAh cm^(−2) at 5 mA cm^(−2).In addition,a O-CNT@Zn||Mn^(2+)inserted hydrated vanadium pentoxide(MnVOH)full cell has a better rate per-formance than a Zn||MnVOH cell,achieving a high discharge capacity of 194 mAh g^(−1) at a high current density of 8 A g^(−1).In a long-term cycling test,the O-CNT@Zn||MnVOH full cell has a capacity retention of 58.8%after 2000 cycles at a current density of 5 A·g^(−1).
基金National Key R&D Program of China (2021YFA1201503)National Natural Science Foundation of China (21972164, 22279161, 12264038, 22309144)+4 种基金Natural Science Foundation of Jiangsu Province (BK. 20210130)China Postdoctoral Science Foundation (2023M733189)Jiangsu Double-Innovation PhD Program in 2022 (JSSCBS20221241)Senior Talents Fund of Jiangsu University (5501220014)fellowship funding provided by the Alexander von Humboldt Foundation。
文摘Rechargeable aqueous zinc-metal batteries (AZMBs) are promising candidates for large-scale energy storage systems due to their low cost and high safety.However,their performance and sustainability are significantly hindered by the sluggish desolvation kinetics at the electrode/electrolyte interface and the corresponding hydrogen evolution reaction where active water molecules tightly participate in the Zn(H_(2)O)_(6)^(2+)solvation shell.Herein,learnt from self-generated solid electrolyte interphase (SEI) in anodes,the dielectric but ion-conductive zinc niobate nanoparticles artificial layer is constructed on metallic Zn surface (ZNB@Zn),acting as a rapid desolvation promotor.The zincophilic and dielectric-conductive properties of ZNB layer accelerate interfacial desolvation/diffusion and suppress surface corrosion or dendrite formation,achieving uniform Zn plating/stripping behavior,as confirmed by electronic/optical microscopies and interface spectroscopical measurements together with theoretical calculations.Consequently,the as-prepared ZNB@Zn electrode exhibits excellent cycling stability of over 2000 h and robust reversibility (99.54%) even under high current density and depth of discharge conditions.Meanwhile,the assembled ZNB@Zn-based full cell displays high capacity-retention rate of 80.21%after 3000 cycles at 5 A g^(-1)and outstanding rate performance up to 10 A g^(-1).The large-areal pouch cell is stabilized for hundreds of cycles,highlighting the bright prospects of the dielectric but ion-conductive layer in further application of AZMBs.
基金National Natural Science Foundation of China (52003191,5247317, 52473275)Young Elite Scientists Sponsorship Program by CAST (2022QNRC001)+3 种基金Natural Science Foundation of Jiangsu Province (BK20221539)Postgraduate Research&Practice Innovation Program of Jiangsu Province (KYCX22_2341)Program of Introducing Talents of Jiangnan University (1065219032210150)Program of China Scholarship Council (202306790065)。
文摘Flexible Zn-based batteries have attracted increasing research interest as essential components of wearable energy storage devices.However,the advancement of flexible aqueous Zn-based batteries based on Co-Ni layered double hydroxide (CoNi-LDH) as the cathode material is hampered by their poor cycling stability and the corrosiveness of alkaline electrolytes.Herein,CoNi-LDH nanosheets enriched with H vacancies (CoNi-LDH(v)) were constructed on a flexible carbon cloth (CC) substrate via electrochemical deposition and activation.The Zn-based battery comprising CoNi-LDH(v)@CC as the cathode exhibited highly reversible conversion reactions and stable operation in 3 M ZnSO4electrolyte (pH=4).The battery delivered an excellent specific capacity (225 mA h g^(-1),0.26 mA h cm^(-2)),acceptable cycling stability(53.9%,900 cycles),and high discharging voltage.The abundant H vacancies served as active sites for the reversible intercalation of Zn^(2+)and the extravasation of NO_(3)-generated channels and space for Zn^(2+)transport and storage,together enabling an excellent Zn^(2+)storage capacity.Furthermore,a sandwich-structured solid-state CoNi-LDH(v)@CC//Zn@CC battery was fabricated and was found to exhibit a noteworthy electrochemical performance and mechanical durability.As a proof of concept,the unencapsulated battery powered a digital watch under various deformation conditions and operated stably for 80 h.Additionally,the flexible battery displayed outstanding customizability,maintaining an open-circuit voltage of 1.42 V even after being cut twice.The proposed engineering strategy contributes to the realization of textiles with truly wearable energy-storage devices.
文摘ZnS ∶Cu nanoparticles were prepared by using microemulsion method at room temperature. The size of the particles is 2-8 nm by transmission electron microscopy (TEM) and dynamic light scattering (DLS) technique. X-ray diffraction analysis shows that the particles are cubic crystal structure, the same structure as the bulk ZnS materials. Ultraviolet absorption demonstrates an increased bandgap due to quantum confinement effect. Photoluminescence spectrum shows there is a single green emission band at 482 nm.
文摘锂硫电池由于其高能量密度、低成本效益被认为是最有前途的下一代电池体系之一.然而多硫化物的穿梭效应大幅降低了锂硫电池的循环稳定性和寿命,严重阻碍其实际应用.无机金属化合物材料改性的隔膜不仅能抑制多硫化锂(LiPS)的穿梭效应,其部分特殊的晶面还能加速多硫化物的氧化还原反应动力学.本文在罗盘状ZnS表面原位生长球状的MoO_(2),制备MoO_(2)/ZnS复合材料.MoO_(2)对多硫化物有着较强的吸附作用,ZnS有着良好的电导率,两者的复合可加速电子传导效率和氧化还原速率.以所制备的MoO_(2)/ZnS作为隔膜改性材料,锂硫电池在5 C的大电流密度下,经过1000次循环后仍可以保持690 mAh g^(-1)的放电比容量,平均每圈的容量衰减率仅为0.014%,表现出优异的循环性能和倍率性能.
