Magnesium hydride serves as a promising solid-state hydrogen storage material owing to its high potential.However,its practical applications are constrained by the high enthalpy of hydrogen absorption and slow kinetic...Magnesium hydride serves as a promising solid-state hydrogen storage material owing to its high potential.However,its practical applications are constrained by the high enthalpy of hydrogen absorption and slow kinetics.In this study,we prepared a Ni/Ti3O5@graphene oxide(GO)dual-heterojunction composite material via solvent heating,electrostatic adsorption,and calcination to improve the hydrogen storage capabilities of MgH2.Adding Ni/Ti3O5@GO to MgH2 lowered the initial dehydrogenation temperature of MgH2 to 183℃;at a dehydrogenation temperature of 275℃,6.4 wt.%of H2 escaped from the MgH2 bulk.In addition,the hydrogen storage material absorbed 1.8 wt.%H2 at 30℃ for 30 min.The calculated activation energy of dehydrogenation was 48.221±0.141 kJ·mol-1,which was significantly lower than that of the ball-milled MgH2(112.63±1.44 kJ·mol-1).Mechanistic analysis results revealed that the heterojunction constructed from the multiphase compound system provided a large number of active sites and hydrogen diffusion routes,resulting in a synergistic catalytic effect that enhanced the hydrogen storage capacity of MgH2.In this work,we clarified the compositions of fuzzy interfaces in heterostructured materials by conducting ultraviolet photoelectron spectroscopy tests and identified key composite materials for the formation of heterojunctions.展开更多
构建准确可靠的热力学数据库对提钒过程优化以及钒酸盐材料的制备具有重要的应用价值和指导意义。采用封闭铂金坩埚,结合X射线衍射(XRD)与差热分析(DTA)技术,证实了K2O-V2O5体系中K3V5O14为稳定存在的化合物,并试验...构建准确可靠的热力学数据库对提钒过程优化以及钒酸盐材料的制备具有重要的应用价值和指导意义。采用封闭铂金坩埚,结合X射线衍射(XRD)与差热分析(DTA)技术,证实了K2O-V2O5体系中K3V5O14为稳定存在的化合物,并试验测定了K2V8O21和KVO3的熔化温度分别为532.4℃和516.5℃。随后采用修正的准化学模型(MQM),引入溶液中第二相邻阳离子短程有序对描述吉布斯自由能的变化。基于CALPHAD框架(CALculation of PHAse Diagram,相图计算),构建了Na2O-K2O-V2O5体系的热力学模型,重现了Na2O-K2O-V2O5体系全组分范围的实验数据和热力学性质,获得了该体系中所有物相一系列自洽的热力学模型参数,最终构建了可靠的热力学数据库。进一步探讨了当前数据库在钒渣钠化焙烧提钒中的应用,明确了含钒物相的迁移规律,确定了最佳的操作温度窗口。展开更多
Zn-based thermal charging devices,utilizing the synergistic effect of ion thermoextraction and thermodiffusion,are able to efficiently convert thermal energy into electrical energy and storage in the devices,making th...Zn-based thermal charging devices,utilizing the synergistic effect of ion thermoextraction and thermodiffusion,are able to efficiently convert thermal energy into electrical energy and storage in the devices,making them a highly promising technology for low-grade heat recovery and utilization.However,the low output power density and energy conversion efficiency resulted by the slow diffusion kinetics of Zn2+hinder their development.Herein,we present a highperformance thermal charging cell design using Zn2+/NH4+hybrid ion electrolyte,which not only maintains the high output voltage of the Zn-based thermoelectric system,but also significantly enhances the output power density due to the fast diffusion kinetics of NH4+.Based on this strategy,the thermal charging cell displays a high thermopower of 12.5 mV K-1and an excellent normalized power density of 19.6 mW m-2K-2at a temperature difference of 35 K.The Carnot-relative efficiency is as high as 12.74%.Moreover,it can operate continuously for over 72 h when the temperature difference persists,achieving a balance between thermoelectric conversion and output.This work provides a simple and effective strategy for the design of high-performance thermal charging cells for low-grade heat conversion and utilization.展开更多
A multi-phase slag containing Na2O is potential to efficiently dephosphorize high-P hot metal.After dephosphorization,the generated slag with high P2O5 content is regarded as a P resource.Because P2O5 was mainly conce...A multi-phase slag containing Na2O is potential to efficiently dephosphorize high-P hot metal.After dephosphorization,the generated slag with high P2O5 content is regarded as a P resource.Because P2O5 was mainly concentrated in the 2CaO SiO2-3CaO P2O5 solid solution,the recovery of P from dephosphorization slag primarily depends on the separation of the solid solution from other phases.The distribution ratios of P2O5 between solid solution and liquid phase in the CaOSiO2-FeO-P2O5-Nslag system were investigated.The results indicated that the addition of Na2O facilitated the enrichment of P2O5 in the solid solution because it increased not only the distribution ratio of P2O5 but also the mass fraction of the solid solution.The distribution ratio of P2O5 was independent of the P2O5 content in slag.A higher P2O5 content in slag resulted in higher P2O5 and Na2O contents in the solid solution.The distribution ratio of P2O5 increased with the total Fe content in the liquid phase,regardless of the valence of Fe.An increase in the FeO content in slag brought a higher P2O5 content in the solid solution.As slag basicity increased,the distribution ratio of P2O5 increased,but the P2O5 content in the solid solution decreased.展开更多
The lack of thermodynamic information,such as primary phase fields and liquidus temperatures,in the CaO-SiO2-Nb2O5-La2O3 quaternary system phase diagram has restricted the comprehensive utilization of the niobium(Nb) ...The lack of thermodynamic information,such as primary phase fields and liquidus temperatures,in the CaO-SiO2-Nb2O5-La2O3 quaternary system phase diagram has restricted the comprehensive utilization of the niobium(Nb) and rare earth(RE) resources.In this work,the phase equilibria in low basicity region(w(CaO)/w(SiO2)<1) of CaO-SiO2-Nb2O5-(0-15 wt%)La2O3 system at 1373-1873 K were experimentally studied by thermodynamic equilibrium experiment,and then,the results were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometry(EDS).Additionally,an optimized method was proposed to process the compositions of equilibrium liquid phases at different temperatures.According to the experimental results,the univariate line between CaNb2O6,SiO2 and LaNbO4 primary phase fields,interface between CaNb2O6 and SiO2 primary phase fields and isothermal liquidus surfaces in SiO2 primary phase field were determined.Finally,the spatial phase diagram of CaO-SiO2-Nb2O5-La2O3 within specific region was constructed,and furthermore,the phase diagram was also presented in CaO-SiO2-Nb2O5 pseudo-ternary system with w(La2O3)=5 wt%,10 wt% and 15 wt%.The research results have guiding significance for the improvement of related phase diagram and the comprehensive utilization of Nb and RE resources.展开更多
基金supported by the National Natural Science Foundation of China[grant number U24A2044]Science and Technology Major Program of Guangxi Province[grant number GUIKEAA24206007].
摘要Magnesium hydride serves as a promising solid-state hydrogen storage material owing to its high potential.However,its practical applications are constrained by the high enthalpy of hydrogen absorption and slow kinetics.In this study,we prepared a Ni/Ti3O5@graphene oxide(GO)dual-heterojunction composite material via solvent heating,electrostatic adsorption,and calcination to improve the hydrogen storage capabilities of MgH2.Adding Ni/Ti3O5@GO to MgH2 lowered the initial dehydrogenation temperature of MgH2 to 183℃;at a dehydrogenation temperature of 275℃,6.4 wt.%of H2 escaped from the MgH2 bulk.In addition,the hydrogen storage material absorbed 1.8 wt.%H2 at 30℃ for 30 min.The calculated activation energy of dehydrogenation was 48.221±0.141 kJ·mol-1,which was significantly lower than that of the ball-milled MgH2(112.63±1.44 kJ·mol-1).Mechanistic analysis results revealed that the heterojunction constructed from the multiphase compound system provided a large number of active sites and hydrogen diffusion routes,resulting in a synergistic catalytic effect that enhanced the hydrogen storage capacity of MgH2.In this work,we clarified the compositions of fuzzy interfaces in heterostructured materials by conducting ultraviolet photoelectron spectroscopy tests and identified key composite materials for the formation of heterojunctions.
摘要构建准确可靠的热力学数据库对提钒过程优化以及钒酸盐材料的制备具有重要的应用价值和指导意义。采用封闭铂金坩埚,结合X射线衍射(XRD)与差热分析(DTA)技术,证实了K2O-V2O5体系中K3V5O14为稳定存在的化合物,并试验测定了K2V8O21和KVO3的熔化温度分别为532.4℃和516.5℃。随后采用修正的准化学模型(MQM),引入溶液中第二相邻阳离子短程有序对描述吉布斯自由能的变化。基于CALPHAD框架(CALculation of PHAse Diagram,相图计算),构建了Na2O-K2O-V2O5体系的热力学模型,重现了Na2O-K2O-V2O5体系全组分范围的实验数据和热力学性质,获得了该体系中所有物相一系列自洽的热力学模型参数,最终构建了可靠的热力学数据库。进一步探讨了当前数据库在钒渣钠化焙烧提钒中的应用,明确了含钒物相的迁移规律,确定了最佳的操作温度窗口。
基金supported by the Leading Edge Technology of Jiangsu Province(BK20222009-X.Z.,BK20202008-X.Z.)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)National Undergraduate Innovation Training Program of NUAA(202410287179Y).
摘要Zn-based thermal charging devices,utilizing the synergistic effect of ion thermoextraction and thermodiffusion,are able to efficiently convert thermal energy into electrical energy and storage in the devices,making them a highly promising technology for low-grade heat recovery and utilization.However,the low output power density and energy conversion efficiency resulted by the slow diffusion kinetics of Zn2+hinder their development.Herein,we present a highperformance thermal charging cell design using Zn2+/NH4+hybrid ion electrolyte,which not only maintains the high output voltage of the Zn-based thermoelectric system,but also significantly enhances the output power density due to the fast diffusion kinetics of NH4+.Based on this strategy,the thermal charging cell displays a high thermopower of 12.5 mV K-1and an excellent normalized power density of 19.6 mW m-2K-2at a temperature difference of 35 K.The Carnot-relative efficiency is as high as 12.74%.Moreover,it can operate continuously for over 72 h when the temperature difference persists,achieving a balance between thermoelectric conversion and output.This work provides a simple and effective strategy for the design of high-performance thermal charging cells for low-grade heat conversion and utilization.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.51704010,51604003,U1760117)Key Laboratory Open Project Fund of Metallurgical Emission Reduction and Resources Recycling(Anhui University of Technology)Ministry of Education(JKF18-02).
摘要A multi-phase slag containing Na2O is potential to efficiently dephosphorize high-P hot metal.After dephosphorization,the generated slag with high P2O5 content is regarded as a P resource.Because P2O5 was mainly concentrated in the 2CaO SiO2-3CaO P2O5 solid solution,the recovery of P from dephosphorization slag primarily depends on the separation of the solid solution from other phases.The distribution ratios of P2O5 between solid solution and liquid phase in the CaOSiO2-FeO-P2O5-Nslag system were investigated.The results indicated that the addition of Na2O facilitated the enrichment of P2O5 in the solid solution because it increased not only the distribution ratio of P2O5 but also the mass fraction of the solid solution.The distribution ratio of P2O5 was independent of the P2O5 content in slag.A higher P2O5 content in slag resulted in higher P2O5 and Na2O contents in the solid solution.The distribution ratio of P2O5 increased with the total Fe content in the liquid phase,regardless of the valence of Fe.An increase in the FeO content in slag brought a higher P2O5 content in the solid solution.As slag basicity increased,the distribution ratio of P2O5 increased,but the P2O5 content in the solid solution decreased.
基金Project supported by the National Key R&D Program of China(2017YFC0805100)the National Natural Science Foundation of China(51774087)the Fundamental Research Funds for the Central Universities China(N162506002)
摘要The lack of thermodynamic information,such as primary phase fields and liquidus temperatures,in the CaO-SiO2-Nb2O5-La2O3 quaternary system phase diagram has restricted the comprehensive utilization of the niobium(Nb) and rare earth(RE) resources.In this work,the phase equilibria in low basicity region(w(CaO)/w(SiO2)<1) of CaO-SiO2-Nb2O5-(0-15 wt%)La2O3 system at 1373-1873 K were experimentally studied by thermodynamic equilibrium experiment,and then,the results were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometry(EDS).Additionally,an optimized method was proposed to process the compositions of equilibrium liquid phases at different temperatures.According to the experimental results,the univariate line between CaNb2O6,SiO2 and LaNbO4 primary phase fields,interface between CaNb2O6 and SiO2 primary phase fields and isothermal liquidus surfaces in SiO2 primary phase field were determined.Finally,the spatial phase diagram of CaO-SiO2-Nb2O5-La2O3 within specific region was constructed,and furthermore,the phase diagram was also presented in CaO-SiO2-Nb2O5 pseudo-ternary system with w(La2O3)=5 wt%,10 wt% and 15 wt%.The research results have guiding significance for the improvement of related phase diagram and the comprehensive utilization of Nb and RE resources.