Aqueous Zn-ion batteries(AZIBs)are one of the promising battery technologies for the green energy storage and electric vehicles.As one attractive cathode material for AZIBs,α-MnO2 materials exhibit superior electroch...Aqueous Zn-ion batteries(AZIBs)are one of the promising battery technologies for the green energy storage and electric vehicles.As one attractive cathode material for AZIBs,α-MnO2 materials exhibit superior electrochemical properties.However,their long-term reversibility is still in great suspense.Considering the decisive effect of the structure and morphology on theα-MnO2 materials,hierarchicalα-MnO2 materials would be promising to improve the cycle performance of AZIB.Here,we synthesized theα-MnO2 urchin-like microspheres(AUM)via a self-assembled method.The porous microspheres composed of one-dimensionalα-MnO2 nanofibers with high crystallinity,which improved the surface area and active sites for Zn2+intercalation.The AUM-based AZIB realized a high initial capacity of 308.0 mA hg-1,and the highest energy density was 396.7 W hkg-1.The kinetics investigation confirmed the high capacitive contribution and fast ion diffusion of the AUM.Ex-situ XRD measurement further verified the synergistic insertion/extraction of H+and Zn2+ions during the charge/discharge process.The superiority of the AUM guaranteed good electrochemical performance and reversible phase evolution,and this application would promote the follow-up research on the advanced AZIB.展开更多
Hierarchical urchin-like gamma-Al2O3 hollow microspheres were prepared by a hydrothermal method followed by a calcination process using Al(NO3)(3)center dot 9H(2)O as aluminum source, NH3 center dot H2O as precipitati...Hierarchical urchin-like gamma-Al2O3 hollow microspheres were prepared by a hydrothermal method followed by a calcination process using Al(NO3)(3)center dot 9H(2)O as aluminum source, NH3 center dot H2O as precipitating agent, and P123 as structure-directing agent (SDA). The obtained samples were investigated using X-ray diffraction (XRD), filed emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and N-2 adsorption/desorption. The influences of P123 concentration, acidic condition, and hydrothermal time on the morphology of product were discussed. P123 has a great influence on ruling the oriented attachment of nanowires and stabilizing the superstructure in the self-assembly process. The 3D urchin-like hollow microspheres have a surface area of 210.2 m(2)/g and the average pore size is 11.42 nm, which have widely potential application such as catalyst, adsorption, and separation.展开更多
Rechargeable Li-O2 batteries (LOBs) have been receiving intensive attention because of their ultra-high theoretical energy densityclose to the gasoline. Herein, Ag modified urchin-like α-MnO2 (Ag-MnO2) material with ...Rechargeable Li-O2 batteries (LOBs) have been receiving intensive attention because of their ultra-high theoretical energy densityclose to the gasoline. Herein, Ag modified urchin-like α-MnO2 (Ag-MnO2) material with hierarchical porous structure is obtained bya facile one-step hydrothermal method. Ag-MnO2 possesses thick nanowires and presents hierarchical porous structure of mesoporesand macropores. The unique structure can expose more active sites, and provide continuous pathways for O2 and discharge productsas well. The doping of Ag leads to the change of electronic distribution in α-MnO2 (i.e., more oxygen vacancies), which playimportant roles in improving their intrinsic catalytic activity and conductivity. As a result, LOBs with Ag-MnO2 catalysts exhibit loweroverpotential, higher discharge specific capacity and much better cycle stability compared to pure a-MnO2. LOBs with Ag-MnO2catalysts exhibit a superior discharge specific capacity of 13,131 mA·h·g^-1 at a current density of 200 mA·h·g^-1, a good cycle stabilityof 500 cycles at the capacity of 500 mA·h·g^-1. When current density is increased to 400 mA·h·g^-1, LOBs still retain a long lifespan of170 cycles at a limited capacity of 1,000 mA·h·g^-1.展开更多
MnO2 microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO2 catalysts were synthesized using the sol-gel method. We obtained three MnO2 microspheres and Au/MnO2 samp...MnO2 microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO2 catalysts were synthesized using the sol-gel method. We obtained three MnO2 microspheres and Au/MnO2 samples： coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO2 are the main factor affecting the catalytic activities of these samples, and γ- MnO2 shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO2. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO2. We also studied intermediate species. The dioxymethylene （DOM） and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO2. A proposed mechanism of formaldehyde oxidation over Au/MnO2 catalysts was also obtained.展开更多
基金supported by the National Key Research and Development Program of China(2016YFA0202400)the 111 Project(B16016)+1 种基金the National Natural Science Foundation of China(51702096,U1705256 and 51572080)the Fundamental Research Funds for the Central Universities(2018ZD07 and JB2019132)。
文摘Aqueous Zn-ion batteries(AZIBs)are one of the promising battery technologies for the green energy storage and electric vehicles.As one attractive cathode material for AZIBs,α-MnO2 materials exhibit superior electrochemical properties.However,their long-term reversibility is still in great suspense.Considering the decisive effect of the structure and morphology on theα-MnO2 materials,hierarchicalα-MnO2 materials would be promising to improve the cycle performance of AZIB.Here,we synthesized theα-MnO2 urchin-like microspheres(AUM)via a self-assembled method.The porous microspheres composed of one-dimensionalα-MnO2 nanofibers with high crystallinity,which improved the surface area and active sites for Zn2+intercalation.The AUM-based AZIB realized a high initial capacity of 308.0 mA hg-1,and the highest energy density was 396.7 W hkg-1.The kinetics investigation confirmed the high capacitive contribution and fast ion diffusion of the AUM.Ex-situ XRD measurement further verified the synergistic insertion/extraction of H+and Zn2+ions during the charge/discharge process.The superiority of the AUM guaranteed good electrochemical performance and reversible phase evolution,and this application would promote the follow-up research on the advanced AZIB.
基金This work was financially supported by National Natural Science Foundation of China，State Key Laboratory of Advanced Technology for Materials Synthesis and Processing (Wuhan University of Technology)
文摘Hierarchical urchin-like gamma-Al2O3 hollow microspheres were prepared by a hydrothermal method followed by a calcination process using Al(NO3)(3)center dot 9H(2)O as aluminum source, NH3 center dot H2O as precipitating agent, and P123 as structure-directing agent (SDA). The obtained samples were investigated using X-ray diffraction (XRD), filed emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and N-2 adsorption/desorption. The influences of P123 concentration, acidic condition, and hydrothermal time on the morphology of product were discussed. P123 has a great influence on ruling the oriented attachment of nanowires and stabilizing the superstructure in the self-assembly process. The 3D urchin-like hollow microspheres have a surface area of 210.2 m(2)/g and the average pore size is 11.42 nm, which have widely potential application such as catalyst, adsorption, and separation.
基金This work was financially supported by High-level Talents'Discipline Construction Fund of Shandong University(No.31370089963078)Shandong Provincial Science and Technology Major Project(Nos.2016GGX104001,2017CXGC1010,and 2018JMRH0211)+2 种基金the Fundamental Research Funds of Shandong University(Nos.2016JC005,2017JC042 and 2017JC010)the Natural Science Foundation of Shandong Province(No.ZR2017MEM002)School Research Startup Expenses of Harbin Institute of Technology(Shenzhen)(No.DD29100027).
文摘Rechargeable Li-O2 batteries (LOBs) have been receiving intensive attention because of their ultra-high theoretical energy densityclose to the gasoline. Herein, Ag modified urchin-like α-MnO2 (Ag-MnO2) material with hierarchical porous structure is obtained bya facile one-step hydrothermal method. Ag-MnO2 possesses thick nanowires and presents hierarchical porous structure of mesoporesand macropores. The unique structure can expose more active sites, and provide continuous pathways for O2 and discharge productsas well. The doping of Ag leads to the change of electronic distribution in α-MnO2 (i.e., more oxygen vacancies), which playimportant roles in improving their intrinsic catalytic activity and conductivity. As a result, LOBs with Ag-MnO2 catalysts exhibit loweroverpotential, higher discharge specific capacity and much better cycle stability compared to pure a-MnO2. LOBs with Ag-MnO2catalysts exhibit a superior discharge specific capacity of 13,131 mA·h·g^-1 at a current density of 200 mA·h·g^-1, a good cycle stabilityof 500 cycles at the capacity of 500 mA·h·g^-1. When current density is increased to 400 mA·h·g^-1, LOBs still retain a long lifespan of170 cycles at a limited capacity of 1,000 mA·h·g^-1.
基金This work is financially supported by the National Natural Science Foundation of China （Grant Nos. 21107124 and 21337003）, Dean＇s Award Startup Funds of the Chinese Academy of Sciences, the National High Technology Research and Development Program of China （No. 2012AA063101）, and Science Promotion Program of Research Center for Eco-Environmcntal Sciences, CAS （YSW2013B05）.
文摘MnO2 microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO2 catalysts were synthesized using the sol-gel method. We obtained three MnO2 microspheres and Au/MnO2 samples： coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO2 are the main factor affecting the catalytic activities of these samples, and γ- MnO2 shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO2. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO2. We also studied intermediate species. The dioxymethylene （DOM） and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO2. A proposed mechanism of formaldehyde oxidation over Au/MnO2 catalysts was also obtained.
