A novel solid-gas reaction preparation technology was used to adjust the composition and microstructure of the composite crystal materials by changing the preparation parameters. Compared with the commonly used sol-ge...A novel solid-gas reaction preparation technology was used to adjust the composition and microstructure of the composite crystal materials by changing the preparation parameters. Compared with the commonly used sol-gel method, acid base neutralization sedimentation method, hydrothermal method, and gas phase deposition method, the technology was relatively simplified and the elemental composition was controllable, without the use of openings and additives. A kind of multi-element composite porous metal oxide was obtained by pre-intercalation and decarburization. In order to increase the porosity of MoO3 material and promote the adsorption and diffusion of reactant molecules, the microstructure of MoO3 was studied. The preparation process of porous molybdenum trioxide by solid gas combination process was discussed, which provides an innovative idea for the design and preparation of new materials with a large specific surface area and other desirable properties.展开更多
X-ray photoelectron spectroscopy(XPS) and extended X-ray absorption fine structure(EXAFS) were used to characterize the structure of the mixture of molybdenum oxide and anatase calcined at 723 K. The results indicate ...X-ray photoelectron spectroscopy(XPS) and extended X-ray absorption fine structure(EXAFS) were used to characterize the structure of the mixture of molybdenum oxide and anatase calcined at 723 K. The results indicate that molybdenum oxide can disperse onto the surface of anatase(TiO 2) and the dispersion threshold is 11.2 mg in per gram of MoO 3 or 4.8 Mo atoms/nm 2 TiO 2. When the content of MoO 3 is below the dispersion threshold, MoO 3 species is in highly dispersed state interacting strongly with TiO 2 support and in discrete tetrahedral coordination, [MoO 4], on the surface of TiO 2. When the MoO 3 loading is above this value, MoO 3 exists in both dispersed phase and crystalline phase. MoO 3 in dispersed phase is still a discrete [MoO 4] tetrahedron; MoO 3 in crystal phase is in octahedral coordination.展开更多
A simple method is introduced for the preparation of large-area films of molybdenum trioxide (MoO3) microbelts. It is found that such films can be grown on indium tin oxide (ITO) glasses or silicon substrates at l...A simple method is introduced for the preparation of large-area films of molybdenum trioxide (MoO3) microbelts. It is found that such films can be grown on indium tin oxide (ITO) glasses or silicon substrates at low temperatures by thermal evaporation deposition in air without using catalyst. Field emission measurements show that the turn-on field of the MoO3 microbelts is as low as 2.2 V/μm required to obtain a current density of 10 μA/cm^2, The combination of the simplicity of the growth method and the attractive field emission performance makes it a potential low-cost technique for the preparation of large-area field emission cold cathode material.展开更多
Bromine has attracted significant attention as a cathode material for aqueous batteries due to its high reduction potential of 1.05 V(Br_(3)^(-)+2e~-■3Br~-),impressive theoretical specific capacity of 223 mA h g^(-1)...Bromine has attracted significant attention as a cathode material for aqueous batteries due to its high reduction potential of 1.05 V(Br_(3)^(-)+2e~-■3Br~-),impressive theoretical specific capacity of 223 mA h g^(-1),and rapid reaction kinetics in the electrolyte.However,searching for compatible anode materials to match with bromine has posed a challenge due to its highly corrosive nature.In this study,we developed oxygen-deficient MoO_(3) with TiO_(2) coating(referred to as MoO_(3-x)@TiO_(2))as an anode material to pair with a bromine cathode in static full batteries.The oxygen deficiency contributes to enhanced electronic and protonic diffusion within the MoO_(3-x)lattice,while the TiO_(2) coating mitigates structural dissolution and proton trapping during cycling.The MoO_(3-x)@TiO_(2) demonstrates fast charge storage kinetics and excellent resistance to bromine corrosion.The impressive compatibility between MoO_(3-x)@TiO_(2) and bromine enables the construction of membrane-less full batteries with exceptional rate capability and cyclic stability.The MoO_(3-x)@TiO_(2)-bromine battery achieves an energy density of70.8 W h kg^(-1)at a power density of 328.1 W kg^(-1),showcasing an impressive long-term cyclic life of 20,000 cycles.Our study provides valuable insights for the development of high-performance aqueous secondary batteries.展开更多
Molybdenum trioxide(MoO3)is regarded as a promising electrode material for lithium(Li)-ion batteries because of its unique layered structure with a high theoretical capacity(~1117 mAh·g-1).Till now,numerous resea...Molybdenum trioxide(MoO3)is regarded as a promising electrode material for lithium(Li)-ion batteries because of its unique layered structure with a high theoretical capacity(~1117 mAh·g-1).Till now,numerous researches have focused on tuning MoO3 morphology to improve its electrochemical performance.However,the fabrication of MoO3 with a two-dimensional(2D)nanosheet clusters structure has yet been achieved.Here,we report a facile one-step solvothermal method to prepare MoO3 nanosheets,of which the morphology can be facilely tuned via the dose of hydrogen peroxide.Both the experimental results and theoretical calculation suggest that the resultant 2D nanosheets structure could reduce the diffusion paths,which is beneficial for the intercalation of Li-ion.As a result,the nanosheets assembled Li-ion battery has a reversible specific capacity of 756.1 mAh·g-1 at 0.5·g-1,and maintained at 214.7 mAh·g-1 after 600 cycles at a current density of 1 A·g-1with the Coulombic efficiency as high as 97.17%.展开更多
MoO_(3) is one of the most promising anode materials for aqueous aluminum batteries due to its high theoretical capacity and suitable aluminum insertion/de-insertion potential.However,the inferior cycling stability li...MoO_(3) is one of the most promising anode materials for aqueous aluminum batteries due to its high theoretical capacity and suitable aluminum insertion/de-insertion potential.However,the inferior cycling stability limits its further application,and the failure mechanism is still unclear.In this article,we provide a straightforward potential regulation technique to manage phase evolution during the charge/discharge process,which ultimately results in a markedly enhanced MoO_(3) electrode cycling stability.The failure mechanism study reveals that the excessive oxidation of the electrode during charge/discharge generates the H_(0.34)MoO_(3) phase,which has high solubility and is the primary cause of MoO_(3) deactivation.Although the dissolved Mo species will be deposited onto the electrode sheet again,the deposition is not electrochemically active and cannot contribute to the capacitance.Controlling the cutoff potential prevented the production of H_(0.34)MoO_(3),resulting in excellent cycling performance(80.1% capacity retention after 4000 cycles).The as-assembled α-MoO_(3)//MnO_(2) full battery exhibits high discharge plateaus(1.4 and 0.9 V),large specific capacity(200 mAhg^(-1) at 2 Ag^(-1)),and ultra-high coulombic efficiency(99%).The research presented here may contribute to the development of highly stable electrode materials for aqueous batteries.展开更多
Thermodynamics for reduction of molybdenum oxides by aluminum and silicon were calculated, and the results show that reduction reaction is feasible at a certain temperature region. Compared to the presence of CaO or C...Thermodynamics for reduction of molybdenum oxides by aluminum and silicon were calculated, and the results show that reduction reaction is feasible at a certain temperature region. Compared to the presence of CaO or CaCO3, reduction products of molybdenum trioxide with aluminum and silicon at various temperatures were detected by X-ray diffraction (XRD). Results show that molybdenum trioxide is reduced by aluminum or silicon step by step, and the intermediate product is MOO2. At 1000 ℃, molybdenum trioxide could be reduced to metal Mo by aluminum, and in the presence of CaO, metal Mo as the reduction product appears even at 800 ℃. In contrast, silicon could barely reduce molybdenum trioxide to metal Mo even at 1200℃. In the presence of CaO or CaCO3, reducibility of silicon increases significantly, and the reduction products are metal Mo and MoSi2. Altogether, CaO or CaCO3 performs two major roles in reduction process: restraining sublimation of MoO3 and decreasing the temperature of reducing MoO3 to metal Mo.展开更多
Aqueous zinc-ion batteries(ZIBs) have attracted significant attentions because of low cost and high reliability. However, conventional ZIBs are severely limited by the development of high energy density cathode materi...Aqueous zinc-ion batteries(ZIBs) have attracted significant attentions because of low cost and high reliability. However, conventional ZIBs are severely limited by the development of high energy density cathode materials with reversible Zn^(2+)insertion/extraction. Herein, a conducting polymer intercalated MoO_(3)(PMO) with extensively extended interlayer spacing is developed as a high-performance ZIBs cathode material. The interlayer spacing of PMO is prominently increased which results in an improved Zn^(2+)mobility during charge and discharge process. More significantly, the electrochemical results reveals that the intercalation of PANI facilitates the charge storage and reinforces the layered structure of MoO_(3), leading to a high capacity and good cycling stability. DFT calculation further reveals the intercalation of PANI into MoO_(3)significantly lower Zn^(2+)diffusion barrier. Benefit from these advantages, the ZIBs based on PMO electrode delivers a considerable capacity of 157 m Ah/g at 0.5 A/g and ameliorative stability with 63.4%capacity retention after 1000 cycles.展开更多
基金Funded by National Natural Science Foundation of China(No.516722040)。
文摘A novel solid-gas reaction preparation technology was used to adjust the composition and microstructure of the composite crystal materials by changing the preparation parameters. Compared with the commonly used sol-gel method, acid base neutralization sedimentation method, hydrothermal method, and gas phase deposition method, the technology was relatively simplified and the elemental composition was controllable, without the use of openings and additives. A kind of multi-element composite porous metal oxide was obtained by pre-intercalation and decarburization. In order to increase the porosity of MoO3 material and promote the adsorption and diffusion of reactant molecules, the microstructure of MoO3 was studied. The preparation process of porous molybdenum trioxide by solid gas combination process was discussed, which provides an innovative idea for the design and preparation of new materials with a large specific surface area and other desirable properties.
基金the National Natural Science Foundation of China(No.2 97330 80 ) and the Major State Basic ResearchDevelopment Program(No.G2 0 0 0 0 775 0 3)
文摘X-ray photoelectron spectroscopy(XPS) and extended X-ray absorption fine structure(EXAFS) were used to characterize the structure of the mixture of molybdenum oxide and anatase calcined at 723 K. The results indicate that molybdenum oxide can disperse onto the surface of anatase(TiO 2) and the dispersion threshold is 11.2 mg in per gram of MoO 3 or 4.8 Mo atoms/nm 2 TiO 2. When the content of MoO 3 is below the dispersion threshold, MoO 3 species is in highly dispersed state interacting strongly with TiO 2 support and in discrete tetrahedral coordination, [MoO 4], on the surface of TiO 2. When the MoO 3 loading is above this value, MoO 3 exists in both dispersed phase and crystalline phase. MoO 3 in dispersed phase is still a discrete [MoO 4] tetrahedron; MoO 3 in crystal phase is in octahedral coordination.
基金support of the project from the National Natural Sci-ence Foundation of China(Nos.U0634002,50725206,60571035and50672135)the National Basic ResearchProgram of China(Nos.2003CB314701,2007CB935501and2008AA03A314),the Science and Technology Depart-ment of Guangdong Province,and the Department of Informa-tion Industry of Guangdong Province,and the Science and Technology Department of Guangzhou City
文摘A simple method is introduced for the preparation of large-area films of molybdenum trioxide (MoO3) microbelts. It is found that such films can be grown on indium tin oxide (ITO) glasses or silicon substrates at low temperatures by thermal evaporation deposition in air without using catalyst. Field emission measurements show that the turn-on field of the MoO3 microbelts is as low as 2.2 V/μm required to obtain a current density of 10 μA/cm^2, The combination of the simplicity of the growth method and the attractive field emission performance makes it a potential low-cost technique for the preparation of large-area field emission cold cathode material.
基金the financial support from the National Key Research and Development Program of China(2022YFB2502003)the Guangdong Basic and Applied Basic Research Foundation(2023B1515040011)。
文摘Bromine has attracted significant attention as a cathode material for aqueous batteries due to its high reduction potential of 1.05 V(Br_(3)^(-)+2e~-■3Br~-),impressive theoretical specific capacity of 223 mA h g^(-1),and rapid reaction kinetics in the electrolyte.However,searching for compatible anode materials to match with bromine has posed a challenge due to its highly corrosive nature.In this study,we developed oxygen-deficient MoO_(3) with TiO_(2) coating(referred to as MoO_(3-x)@TiO_(2))as an anode material to pair with a bromine cathode in static full batteries.The oxygen deficiency contributes to enhanced electronic and protonic diffusion within the MoO_(3-x)lattice,while the TiO_(2) coating mitigates structural dissolution and proton trapping during cycling.The MoO_(3-x)@TiO_(2) demonstrates fast charge storage kinetics and excellent resistance to bromine corrosion.The impressive compatibility between MoO_(3-x)@TiO_(2) and bromine enables the construction of membrane-less full batteries with exceptional rate capability and cyclic stability.The MoO_(3-x)@TiO_(2)-bromine battery achieves an energy density of70.8 W h kg^(-1)at a power density of 328.1 W kg^(-1),showcasing an impressive long-term cyclic life of 20,000 cycles.Our study provides valuable insights for the development of high-performance aqueous secondary batteries.
基金financially supported by the National Natural Science Foundation of China(Grant No.51972200)
文摘Molybdenum trioxide(MoO3)is regarded as a promising electrode material for lithium(Li)-ion batteries because of its unique layered structure with a high theoretical capacity(~1117 mAh·g-1).Till now,numerous researches have focused on tuning MoO3 morphology to improve its electrochemical performance.However,the fabrication of MoO3 with a two-dimensional(2D)nanosheet clusters structure has yet been achieved.Here,we report a facile one-step solvothermal method to prepare MoO3 nanosheets,of which the morphology can be facilely tuned via the dose of hydrogen peroxide.Both the experimental results and theoretical calculation suggest that the resultant 2D nanosheets structure could reduce the diffusion paths,which is beneficial for the intercalation of Li-ion.As a result,the nanosheets assembled Li-ion battery has a reversible specific capacity of 756.1 mAh·g-1 at 0.5·g-1,and maintained at 214.7 mAh·g-1 after 600 cycles at a current density of 1 A·g-1with the Coulombic efficiency as high as 97.17%.
基金the Youth Program of National Natural Science Foundation of China(grant nos.21905300,52277229,22109180,and 51877216)Taishan Scholar Foundation(grant no.tspd20210308)+5 种基金National Key Research and Development of China(grant no.2022YFA1503400)Key Projects of Shandong Key R&D plan(grant no.2019JZZY010506)Fundamental Research Funds for the Central Universities(grant no.21CX06011A)111 Program of National College Disciplinary Innovation(grant no.B03031)Natural Science Foundation of Shandong Province(grant nos.ZR202103040491 and ZR2020MB078)Research Project of State Key Laboratory for Heavy Oil Processing(grant no.SLKZZKT-2021).
文摘MoO_(3) is one of the most promising anode materials for aqueous aluminum batteries due to its high theoretical capacity and suitable aluminum insertion/de-insertion potential.However,the inferior cycling stability limits its further application,and the failure mechanism is still unclear.In this article,we provide a straightforward potential regulation technique to manage phase evolution during the charge/discharge process,which ultimately results in a markedly enhanced MoO_(3) electrode cycling stability.The failure mechanism study reveals that the excessive oxidation of the electrode during charge/discharge generates the H_(0.34)MoO_(3) phase,which has high solubility and is the primary cause of MoO_(3) deactivation.Although the dissolved Mo species will be deposited onto the electrode sheet again,the deposition is not electrochemically active and cannot contribute to the capacitance.Controlling the cutoff potential prevented the production of H_(0.34)MoO_(3),resulting in excellent cycling performance(80.1% capacity retention after 4000 cycles).The as-assembled α-MoO_(3)//MnO_(2) full battery exhibits high discharge plateaus(1.4 and 0.9 V),large specific capacity(200 mAhg^(-1) at 2 Ag^(-1)),and ultra-high coulombic efficiency(99%).The research presented here may contribute to the development of highly stable electrode materials for aqueous batteries.
基金financially supported by Hubei Provincial Natural Science Foundation of China (2015CFC838)the Open Research Fund of Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology (No. FMRU201309)
文摘Thermodynamics for reduction of molybdenum oxides by aluminum and silicon were calculated, and the results show that reduction reaction is feasible at a certain temperature region. Compared to the presence of CaO or CaCO3, reduction products of molybdenum trioxide with aluminum and silicon at various temperatures were detected by X-ray diffraction (XRD). Results show that molybdenum trioxide is reduced by aluminum or silicon step by step, and the intermediate product is MOO2. At 1000 ℃, molybdenum trioxide could be reduced to metal Mo by aluminum, and in the presence of CaO, metal Mo as the reduction product appears even at 800 ℃. In contrast, silicon could barely reduce molybdenum trioxide to metal Mo even at 1200℃. In the presence of CaO or CaCO3, reducibility of silicon increases significantly, and the reduction products are metal Mo and MoSi2. Altogether, CaO or CaCO3 performs two major roles in reduction process: restraining sublimation of MoO3 and decreasing the temperature of reducing MoO3 to metal Mo.
基金financially supported by the National Natural Science Foundation of China (Nos. 51771058, 51801030)Natural Science Foundation of Guangdong Province (No. 2018A030310571)。
文摘Aqueous zinc-ion batteries(ZIBs) have attracted significant attentions because of low cost and high reliability. However, conventional ZIBs are severely limited by the development of high energy density cathode materials with reversible Zn^(2+)insertion/extraction. Herein, a conducting polymer intercalated MoO_(3)(PMO) with extensively extended interlayer spacing is developed as a high-performance ZIBs cathode material. The interlayer spacing of PMO is prominently increased which results in an improved Zn^(2+)mobility during charge and discharge process. More significantly, the electrochemical results reveals that the intercalation of PANI facilitates the charge storage and reinforces the layered structure of MoO_(3), leading to a high capacity and good cycling stability. DFT calculation further reveals the intercalation of PANI into MoO_(3)significantly lower Zn^(2+)diffusion barrier. Benefit from these advantages, the ZIBs based on PMO electrode delivers a considerable capacity of 157 m Ah/g at 0.5 A/g and ameliorative stability with 63.4%capacity retention after 1000 cycles.