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
The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)...The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.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 National Natural Science Foundation of China(NSFC)(52203261)Natural Science Foundation of Jiangsu Province(BK20210474)the project of research on the industrial application of"controllable synthesis of nanocarbon-based polymer composites and their application in new energy”(N0.CJGJZD20210408092400002).
文摘The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.
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.
