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
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
Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme hetero...Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.展开更多
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.
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.
文摘Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.
