Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy eff...Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy efficiency.It is,thus,crucial to develop efficient catalysts as well as optimize the solid electrolyte system to unveil potential of the ZAB technology.Due to the low cost and versatility in tailoring the structures and properties,carbon materials have been extensively used as the conductive substrates,catalytic air electrodes,and important components in the electrolytes for the solid‐state ZABs.Within this context,we discuss the challenges facing current solid‐state ZABs and summarize the strategies developed to modify properties of carbon‐based electrodes and electrolytes.We highlight the metal−organic framework/covalent organic framework‐based electrodes,heteroatom‐doped carbon,and the composites formed of carbon with metal oxides/sulfides/phosphides.We also briefly discuss the progress of graphene oxide‐based solid electrolyte.展开更多
果蔬企业在生产过程中会产生大量的果皮,这些废弃物目前还没有得到有效利用。本文以废弃猕猴桃果皮为原料,以氢氧化钾为活化剂,制备了杂原子掺杂多孔碳。通过扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)、拉曼光谱(Ram...果蔬企业在生产过程中会产生大量的果皮,这些废弃物目前还没有得到有效利用。本文以废弃猕猴桃果皮为原料,以氢氧化钾为活化剂,制备了杂原子掺杂多孔碳。通过扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)、拉曼光谱(Raman)和氮气吸附-脱附(BET)等手段对制备的材料进行了表征,结果表明:采用果皮预碳化、活化的方法可以得到N、O、S杂原子原位共掺杂多孔碳;经过氢氧化钾活化后,碳材料的比表面积大幅增加,比表面积最高可达1698.6 m^2/g。在三电极体系下对制备的碳材料超级电容器性能的评价结果表明:在氢氧化钾与猕猴桃果皮质量比1∶3时,电极材料具有最佳的超电性能;在扫描速率为5 m V/s时,材料的比电容为221.1 F/g,同时具有良好的倍率性能和循环稳定性,经过4000次的长循环后,容量保持率为83.2%。展开更多
Boron had been introduced into the structure of carbon material(BC), which was used as the support of Pd catalyst for hydrogenation of 4-carboxybenzaldehyde(4-CBA). The physical properties and chemical composition of ...Boron had been introduced into the structure of carbon material(BC), which was used as the support of Pd catalyst for hydrogenation of 4-carboxybenzaldehyde(4-CBA). The physical properties and chemical composition of the support and corresponding catalyst were characterized by N2 adsorption–desorption,Raman spectroscopy, inductively coupled plasma optical emission spectroscopy(ICP-OES), element analysis(EA), high-resolution transmission electron microscopy(HRTEM), CO-pulse chemisorption and X-ray photoelectron spectroscopy(XPS). The results demonstrate that Pd/BC catalyst exhibits a superior activity and good stability due to the more uniform dispersion of Pd nanoparticles, the presence of mesoporous structure and the enhanced interaction between Pd nanoparticles and the support, compared to carbon and N-doped carbon supported Pd catalysts(Pd/C and Pd/NC, respectively).展开更多
For electric double layer supercapacitors,carbon materials originating from the purely physical energystorage mechanism limit the improvement in the capabilities of charge storage.To solve this problem,doping heteroat...For electric double layer supercapacitors,carbon materials originating from the purely physical energystorage mechanism limit the improvement in the capabilities of charge storage.To solve this problem,doping heteroatoms into carbon skeleton is a promising&charming strategy for enhancing electrochemical performance by providing the extra pseudocapacitance.However,the self-discharge behavior of such heteroatom-doped supercapacitors has been a challenging issue for a long time.Here,the porous carbon nanosheets with a tunable total content of heteroatoms are chosen as a demo to systemically decouple the correlation between the total content of heteroatoms and the specific capacitance as well as the self-discharge behavior.The capacitance changes in a range of 164–331 F g^(-1)@1 A g^(-1)with the increased total contents of doped heteroatom,strongly dependent on and sensitive to the total content of heteroatoms.The voltage retention rate and capacitance retention rate for the porous carbon nanosheets with a tunable total content of heteroatoms completely present a quick decline tendency as the increase in the content of heteroatoms,changing from 58%to 34%and 74%to 39%,respectively,indicative of a linear negative relationship.More importantly,the self-discharge mechanisms are elaborately explored and follow the combination of activation-and diffusion-controlled Faradic reactions.This work illustrates the diverse impacts of the doped heteroatoms on the electrochemical performance of supercapacitors,covering specific capacitance and self-discharge behavior,and highlights the importance of balancing the contents of doped heteroatoms in energy storage fields.展开更多
Transition metal sulfides have been regarded as promising anode materials for sodium-ion batteries(SIB).However,they face the challenges of poor electronic conductivity and large volume change,which result in capacity...Transition metal sulfides have been regarded as promising anode materials for sodium-ion batteries(SIB).However,they face the challenges of poor electronic conductivity and large volume change,which result in capacity fade and low rate capability.In this work,a composite containing ultrasmall CoS(~7 nm)nanoparticles embedded in heteroatom(N,S,and O)-doped carbon was synthesized by an efficient one-step sulfidation process using a Co(Salen)precursor.The ultrasmall CoS nanoparticles are beneficial for mechanical stability and shortening Na-ions diffusion pathways.Furthermore,the N,S,and O-doped defect-rich carbon provides a robust and highly conductive framework enriched with active sites for sodium storage as well as mitigates volume expansion and polysulfide shuttle.As anode for SIB,CoS@HDC exhibits a high initial capacity of 906 mA h g^(-1)at 100 mA g^(-1)and a stable long-term cycling life with over 1000 cycles at 500 mA g^(-1),showing a reversible capacity of 330 mA h g^(-1).Meanwhile,the CoS@HDC anode is proven to maintain its structural integrity and compositional reversibility during cycling.Furthermore,Na-ion full batteries based on the CoS@HDC anode and Na_(3)V_(2)(PO_(4))_(3)cathode demonstrate a stable cycling behavior with a reversible specific capacity of~200 m A h g^(-1)at least for 100 cycles.Moreover,advanced synchrotron operando X-ray diffraction,ex-situ X-ray absorption spectroscopy,and comprehensive electrochemical tests reveal the structural transformation and the Co coordination chemistry evolution of the CoS@HDC during cycling,providing fundamental insights into the sodium storage mechanism.展开更多
基金This study was financially supported by the National Key R&D Research Program of China(Grant No.2018YFB0905400)National Natural Science Foundationof China(Grant Nos.,51925207,U1910210,51972067,51802044,and 51872277)+2 种基金Guangdong Natural Science Funds for Distinguished Young Scholar(Grant No.2019B151502039)Fundamental Research Funds for the Central Universities of China(Grant No.WK2060140026)the DNL Cooperation Fund,CAS(Grant No.DNL180310).
文摘Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy efficiency.It is,thus,crucial to develop efficient catalysts as well as optimize the solid electrolyte system to unveil potential of the ZAB technology.Due to the low cost and versatility in tailoring the structures and properties,carbon materials have been extensively used as the conductive substrates,catalytic air electrodes,and important components in the electrolytes for the solid‐state ZABs.Within this context,we discuss the challenges facing current solid‐state ZABs and summarize the strategies developed to modify properties of carbon‐based electrodes and electrolytes.We highlight the metal−organic framework/covalent organic framework‐based electrodes,heteroatom‐doped carbon,and the composites formed of carbon with metal oxides/sulfides/phosphides.We also briefly discuss the progress of graphene oxide‐based solid electrolyte.
文摘果蔬企业在生产过程中会产生大量的果皮,这些废弃物目前还没有得到有效利用。本文以废弃猕猴桃果皮为原料,以氢氧化钾为活化剂,制备了杂原子掺杂多孔碳。通过扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)、拉曼光谱(Raman)和氮气吸附-脱附(BET)等手段对制备的材料进行了表征,结果表明:采用果皮预碳化、活化的方法可以得到N、O、S杂原子原位共掺杂多孔碳;经过氢氧化钾活化后,碳材料的比表面积大幅增加,比表面积最高可达1698.6 m^2/g。在三电极体系下对制备的碳材料超级电容器性能的评价结果表明:在氢氧化钾与猕猴桃果皮质量比1∶3时,电极材料具有最佳的超电性能;在扫描速率为5 m V/s时,材料的比电容为221.1 F/g,同时具有良好的倍率性能和循环稳定性,经过4000次的长循环后,容量保持率为83.2%。
基金supported by the National Natural Science Foundation of China (No. 21425312 and 21321002)
文摘Boron had been introduced into the structure of carbon material(BC), which was used as the support of Pd catalyst for hydrogenation of 4-carboxybenzaldehyde(4-CBA). The physical properties and chemical composition of the support and corresponding catalyst were characterized by N2 adsorption–desorption,Raman spectroscopy, inductively coupled plasma optical emission spectroscopy(ICP-OES), element analysis(EA), high-resolution transmission electron microscopy(HRTEM), CO-pulse chemisorption and X-ray photoelectron spectroscopy(XPS). The results demonstrate that Pd/BC catalyst exhibits a superior activity and good stability due to the more uniform dispersion of Pd nanoparticles, the presence of mesoporous structure and the enhanced interaction between Pd nanoparticles and the support, compared to carbon and N-doped carbon supported Pd catalysts(Pd/C and Pd/NC, respectively).
基金partly supported by the National Natural Science Foundation of China(51872035,22078052)the Innovation Program of Dalian City of Liaoning Province(2019RJ03)the Shandong Provincial Natural Science Foundation(ZR2020ZD08)。
文摘For electric double layer supercapacitors,carbon materials originating from the purely physical energystorage mechanism limit the improvement in the capabilities of charge storage.To solve this problem,doping heteroatoms into carbon skeleton is a promising&charming strategy for enhancing electrochemical performance by providing the extra pseudocapacitance.However,the self-discharge behavior of such heteroatom-doped supercapacitors has been a challenging issue for a long time.Here,the porous carbon nanosheets with a tunable total content of heteroatoms are chosen as a demo to systemically decouple the correlation between the total content of heteroatoms and the specific capacitance as well as the self-discharge behavior.The capacitance changes in a range of 164–331 F g^(-1)@1 A g^(-1)with the increased total contents of doped heteroatom,strongly dependent on and sensitive to the total content of heteroatoms.The voltage retention rate and capacitance retention rate for the porous carbon nanosheets with a tunable total content of heteroatoms completely present a quick decline tendency as the increase in the content of heteroatoms,changing from 58%to 34%and 74%to 39%,respectively,indicative of a linear negative relationship.More importantly,the self-discharge mechanisms are elaborately explored and follow the combination of activation-and diffusion-controlled Faradic reactions.This work illustrates the diverse impacts of the doped heteroatoms on the electrochemical performance of supercapacitors,covering specific capacitance and self-discharge behavior,and highlights the importance of balancing the contents of doped heteroatoms in energy storage fields.
基金the financial support from China Scholarship Council(202108080263)Financial support by the Federal Ministry of Education and Research(BMBF)under the project“He Na”(03XP0390C)+1 种基金the German Research Foundation(DFG)under the joint German-Russian DFG project“KIBSS”(448719339)are acknowledgedthe financial support from the Federal Ministry of Education and Research(BMBF)under the project“Ka Si Li”(03XP0254D)in the competence cluster“Excell Batt Mat”。
文摘Transition metal sulfides have been regarded as promising anode materials for sodium-ion batteries(SIB).However,they face the challenges of poor electronic conductivity and large volume change,which result in capacity fade and low rate capability.In this work,a composite containing ultrasmall CoS(~7 nm)nanoparticles embedded in heteroatom(N,S,and O)-doped carbon was synthesized by an efficient one-step sulfidation process using a Co(Salen)precursor.The ultrasmall CoS nanoparticles are beneficial for mechanical stability and shortening Na-ions diffusion pathways.Furthermore,the N,S,and O-doped defect-rich carbon provides a robust and highly conductive framework enriched with active sites for sodium storage as well as mitigates volume expansion and polysulfide shuttle.As anode for SIB,CoS@HDC exhibits a high initial capacity of 906 mA h g^(-1)at 100 mA g^(-1)and a stable long-term cycling life with over 1000 cycles at 500 mA g^(-1),showing a reversible capacity of 330 mA h g^(-1).Meanwhile,the CoS@HDC anode is proven to maintain its structural integrity and compositional reversibility during cycling.Furthermore,Na-ion full batteries based on the CoS@HDC anode and Na_(3)V_(2)(PO_(4))_(3)cathode demonstrate a stable cycling behavior with a reversible specific capacity of~200 m A h g^(-1)at least for 100 cycles.Moreover,advanced synchrotron operando X-ray diffraction,ex-situ X-ray absorption spectroscopy,and comprehensive electrochemical tests reveal the structural transformation and the Co coordination chemistry evolution of the CoS@HDC during cycling,providing fundamental insights into the sodium storage mechanism.
