Alkaline water electrolysis(AWE)is the most mature technology for hydrogen production by water electrolysis.Alkaline water electrolyzer consists of multiple electrolysis cells,and a single cell consists of a diaphragm...Alkaline water electrolysis(AWE)is the most mature technology for hydrogen production by water electrolysis.Alkaline water electrolyzer consists of multiple electrolysis cells,and a single cell consists of a diaphragm,electrodes,bipolar plates and end plates,etc.The existing industrial bipolar plate channel is concave-convex structure,which is manufactured by complicated and high-cost mold punching.This structure still results in uneven electrolyte flow and low current density in the electrolytic cell,further increasing in energy consumption and cost of AWE.Thereby,in this article,the electrochemical and flow model is firstly constructed,based on the existing industrial concave and convex flow channel structure of bipolar plate,to study the current density,electrolyte flow and bubble distribution in the electrolysis cell.The reliability of the model was verified by comparison with experimental data in literature.Among which,the electrochemical current density affects the bubble yield,on the other hand,the generated bubbles cover the electrode surface,affecting the active specific surface area and ohmic resistance,which in turn affects the electrochemical reaction.The result indicates that the flow velocity near the bottom of the concave ball approaches zero,while the flow velocity on the convex ball surface is significantly higher.Additionally,vortices are observed within the flow channel structure,leading to an uneven distribution of electrolyte.Next,modelling is used to optimize the bipolar plate structure of AWE by simulating the electrochemistry and fluid flow performances of four kinds of structures,namely,concave and convex,rhombus,wedge and expanded mesh,in the bipolar plate of alkaline water electrolyzer.The results show that the expanded mesh channel structure has the largest current density of 3330 A/m^(2)and electrolyte flow velocity of 0.507 m/s in the electrolytic cell.Under the same current density,the electrolytic cell with the expanded mesh runner structure has the smallest potential and energy consumption.This work provides a useful guide for the comprehensive understanding and optimization of channel structures,and a theoretical basis for the design of large-scale electrolyzer.展开更多
The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past...The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past decades,researchers have reported a number of hydrogen evolution reaction(HER)electrocatalysts with activity comparable to that of commercial Pt/C,but most of them are tested within a small current density range,typically no more than 500 mA cm^(-2).To realize the industrial application of hydrogen production from water electrolysis,it is essential to develop high-efficiency HER electrocatalysts at high current density(HCD≥500 mA cm^(-2)).Nevertheless,it remains challenging and significant to rational design HCD electrocatalysts for HER.In this paper,the design strategy of HCD electrocatalysts is discussed,and some HCD electrocatalysts for HER are reviewed in seven categories(alloy,metal oxide,metal hydroxide,metal sulfide/selenide,metal nitride,metal phosphide and other derived electrocatalysts).At the end of this article,we also pro-pose some viewpoints and prospects for the future development and research directions of HCD electrocatalysts for HER.展开更多
Mg-Li-Gd alloys were prepared by electrochemical codeposition from LiCl-KCl-MgCl 2 -Gd 2 O 3 melts on molybdenum electrode with constant current density at 823 and 973 K. The microstructure of the Mg-Li-Gd alloys was ...Mg-Li-Gd alloys were prepared by electrochemical codeposition from LiCl-KCl-MgCl 2 -Gd 2 O 3 melts on molybdenum electrode with constant current density at 823 and 973 K. The microstructure of the Mg-Li-Gd alloys was analyzed by X-ray diffraction （XRD）, optical microscopy （OM） and scanning electron microscopy （SEM）. The results show that magnesium and gadolinium deposit mainly in the first 30 min, and the alloy obtained contains 96.53% Mg, 0.27% Li and 3.20% Gd （mass fraction）. Then, the reduction of lithium ions occurs quickly. The composition of alloy can be adjusted by controlling electrolysis time or Gd 2 O 3 concentration in LiCl-KCl melts. With the addition of Gd into Mg-Li alloys, the corrosion resistance of the alloys is enhanced. XRD results suggest that Mg 3 Gd and Mg 2 Gd can be formed in Mg-Li-Gd alloys. The distribution of Gd element in Mg-Li-Gd alloys indicates that Gd element mainly distributes at the grain boundaries of Mg-Li-Gd alloys.展开更多
Mg-La alloys were prepared by constant voltage electrolysis in the molten salt system of MgC12-LaC13-KC1 at 750℃, with a graphite crucible as the anode and a tungsten rod as the cathode. The effect of oxide and fluor...Mg-La alloys were prepared by constant voltage electrolysis in the molten salt system of MgC12-LaC13-KC1 at 750℃, with a graphite crucible as the anode and a tungsten rod as the cathode. The effect of oxide and fluoride addition on the electrolysis was investigated comprehensively. X-ray diffraction （XRD） was used to characterize some of the Mg-La alloy products and the sludges. As the content of MgO or La203 in the electrolyte increased, both the current efficiency and the mass of alloy product decreased, indicating that both MgO and La203 may take part in the reactions in the electrolyte. When the same mass of the oxide was added, compared with La203, MgO had a more pronounced effect on both the current efficiency and the mass of alloy product. XRD studies confirmed the formation of LaOC1 when MgO or LazO3 was added into the electrolyte. The formation of LaOCl sludge would be the main reason for the negative effect of the oxide addition on both the current efficiency and the mass of alloy. In the electrolytic system, the addition of CaF2 was not helpful to suppress the negative effect of MgO on the electrolysis, probably due to the complex reactions of the La compounds in the electrolyte.展开更多
Extracting aluminum from aluminum alloys in AlCl3-NaCl molten salts was investigated. Al coating was deposited on the copper cathode by the method of direct current deposition using aluminum alloys as anode. The purit...Extracting aluminum from aluminum alloys in AlCl3-NaCl molten salts was investigated. Al coating was deposited on the copper cathode by the method of direct current deposition using aluminum alloys as anode. The purity of the deposited aluminum is about 99.7% with the energy consumption of 3-9 kW＆#183;h per kg Al, and the current efficiency is 44%-64% when the deposition process is carried out under 100 mA/cm2 for 4 h at 170 ＆#176;C. The effects of experimental parameters, such as molar ratio of AlCl3 to NaCl, cathodic current density and electrolysis time, on the current efficiency were studied. The molar ratio of AlCl3 to NaCl has little effect on the current efficiency, and the increase of deposition temperature is beneficial to the increase of current efficiency. However, the increase of current density or electrolysis time results in the decrease of current efficiency. The decrease of current efficiency is mainly related to the formation of dendritic or powder deposit of aluminum which is easy to fall into the electrolyte.展开更多
Mg-Al-Sn alloy is one of the new developed anode materials for seawater activated batteries. The potentiodynamic polarization, galvanostatic discharge and electrochemical impedance spectroscopy of Mg-6%Al-1%Sn and Mg-...Mg-Al-Sn alloy is one of the new developed anode materials for seawater activated batteries. The potentiodynamic polarization, galvanostatic discharge and electrochemical impedance spectroscopy of Mg-6%Al-1%Sn and Mg-6%Al-5%Sn(mass fraction) alloys in seawater were studied and compared with the commercial AZ31 and AP65 alloys. The results show that the Mg-6%Al-1%Sn alloy obtains the most negative discharge potential of average-1.611V with a electric current density of 100 mA/cm2. EIS studies reveal that the Mg-Al-Sn alloy/seawater interfacial electrochemical process is determined by an activation controlled reaction. The assembled prototype batteries with Mg-6%Al-1%Sn alloy as anodes and Ag Cl as cathodes exhibit a satisfactory integrated discharge properties.展开更多
The electrochemical synthesis silicon wires by electrorefining metallurgical grade silicon in thermally dried and pre-electrolyzed molten KF-NaF eutectic were studied at temperatures 800-900 ℃ using cyclic voltammetr...The electrochemical synthesis silicon wires by electrorefining metallurgical grade silicon in thermally dried and pre-electrolyzed molten KF-NaF eutectic were studied at temperatures 800-900 ℃ using cyclic voltammetry and ac impedance. One oxidation peak at -0.14 V could be attributed to the reaction of Si to Si4＋. A cathodic peak occurred at -0.56 V in the cyclic voltammogram and one response semicircle in the ac impedance spectrum was observed, supporting a one-step electrochemical reduction process of Si4＋-→Si. The electrochemical reaction of silicon was controlled by the diffusion process. The purity of electrorefined silicon wires was up to 99.999% by ICP-MS analysis.展开更多
The physical and mathematical model of an operating electrowinning cell was established, and the flow of electrolyte was numerically simulated by the commercial software Fluent. The results indicate that there are two...The physical and mathematical model of an operating electrowinning cell was established, and the flow of electrolyte was numerically simulated by the commercial software Fluent. The results indicate that there are two circulations at the surface flow where part of electrolyte backflows to the inlet from the side of cell, and the rest flows directly to the outlet, and the separation of two circulations with opposite direction occurs at the 20th pair of anode-cathode. This phenomenon was observed in the real operation. The electrolyte flows into the space between anode and cathode from the side portion of the cell. Meanwhile, the interelectrode effective flow rate （IEFR） is put forward to describe quantitively the flow field characteristics and is defined as the ratio of electrolyte flow between the anode and cathode to the total flow area. The influences of structure parameters and operating conditions on IEFR, such as the inlet angle, the volumetric flow rate, the inlet position and the height of steel baffles were simulated. The inlet position has a significant influence on the IEFR and its optimal value is 0.9 m below free surface. The inlet angle should be in the range from -10° to 10°. IEFR is in linear proportion with the volumetric flow rate, and the height of the steel baffle has little influence on the flow field.展开更多
The corrosion pathways in AA2024-T3, AA5083-O and AA6082-T6 alloys have been investigated. The objective of the investigation is to further the understanding of the complex localised corrosion mechanism in aluminium a...The corrosion pathways in AA2024-T3, AA5083-O and AA6082-T6 alloys have been investigated. The objective of the investigation is to further the understanding of the complex localised corrosion mechanism in aluminium alloys. The investigation was carried out by examining the corroded surfaces of the alloys after potentiodynamic polarization tests in a 3.5% NaCl solution with the aid of a scanning electron microscope, and by analysing the flow of anolyte solution using the scanning vibrating electrode technique. The results revealed that the overall corrosion pathways in the alloys are distinctively different and are influenced by the flow of anolyte solution. Also revealed, was the fact that corrosion propagates in two ways （particularly in the AA5083-O and AA6082-T6 alloys）： an overall pathway in the corrosion front （filiform-like pathway in the AA5083 alloy and organized linear pathways in AA6082 alloy）; and the crystallographic channelling along the （100） directions. These are dependent on the grain distinct features of the AA5083-O and AA6082-T6 alloys and are not influenced by the presence of coarse second phase particles in these alloys, compared with the AA2024-T3 alloy, where the corrosion pathways are more dependent on the presence of second phase particles and grain boundary character.展开更多
文摘采用2种导流方式,即S导流型和E导流型的单室电合成反应器,制备有效面积为438 cm^2的气体扩散电极,研究不同导流方式对气体扩散阴极电合成反应器制备过氧化氢(H2O2)的影响。结果表明,S导流型反应器中,随水力停留时间(Hydraulic Retention Time,HRT)减小,H2O2质量浓度逐渐降低;在电流密度为25 m A/cm^2、HRT为5.7 min时,H2O2质量浓度可达2062 mg/L;当HRT为1.1 min时,H2O2产率可达0.150 kg/(m^2·h);在电流密度为25 m A/cm^2、HRT为1.1 min时,能耗为8.33(k W·h)/kg,电流效率达到90%~93%。E导流型反应器中,在25 m A/cm^2下、HRT=5.7 min时,产生的最大H2O2质量浓度为1693 mg/L;HRT对H2O2产率影响不明显,在25 m A/cm^2、HRT=1.1~2.9min时,H2O2产率平均约为0.125 kg/(m^2·h);HRT的减小不能显著降低能耗,在25 m A/cm^2、HRT=5.7 min时,能耗高达14.66(k W·h)/kg。E导流型反应器性能较差的主要原因在于不能促使阳极气体及时排出,造成H2O2的产率和电流效率均降低。因此,S导流型反应器性能优于E导流型反应器。最大H2O2产率优于文献报道的结果,可归因于较小的极板间距和气体扩散电极表面导流板的共同作用。
基金financially supported by the National Natural Science Foundation of China(No.52074130)the Engineering Research Center of Resource Utilization of Carbon-containing Waste with Carbon Neutrality,Ministry of Education。
文摘Alkaline water electrolysis(AWE)is the most mature technology for hydrogen production by water electrolysis.Alkaline water electrolyzer consists of multiple electrolysis cells,and a single cell consists of a diaphragm,electrodes,bipolar plates and end plates,etc.The existing industrial bipolar plate channel is concave-convex structure,which is manufactured by complicated and high-cost mold punching.This structure still results in uneven electrolyte flow and low current density in the electrolytic cell,further increasing in energy consumption and cost of AWE.Thereby,in this article,the electrochemical and flow model is firstly constructed,based on the existing industrial concave and convex flow channel structure of bipolar plate,to study the current density,electrolyte flow and bubble distribution in the electrolysis cell.The reliability of the model was verified by comparison with experimental data in literature.Among which,the electrochemical current density affects the bubble yield,on the other hand,the generated bubbles cover the electrode surface,affecting the active specific surface area and ohmic resistance,which in turn affects the electrochemical reaction.The result indicates that the flow velocity near the bottom of the concave ball approaches zero,while the flow velocity on the convex ball surface is significantly higher.Additionally,vortices are observed within the flow channel structure,leading to an uneven distribution of electrolyte.Next,modelling is used to optimize the bipolar plate structure of AWE by simulating the electrochemistry and fluid flow performances of four kinds of structures,namely,concave and convex,rhombus,wedge and expanded mesh,in the bipolar plate of alkaline water electrolyzer.The results show that the expanded mesh channel structure has the largest current density of 3330 A/m^(2)and electrolyte flow velocity of 0.507 m/s in the electrolytic cell.Under the same current density,the electrolytic cell with the expanded mesh runner structure has the smallest potential and energy consumption.This work provides a useful guide for the comprehensive understanding and optimization of channel structures,and a theoretical basis for the design of large-scale electrolyzer.
文摘The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past decades,researchers have reported a number of hydrogen evolution reaction(HER)electrocatalysts with activity comparable to that of commercial Pt/C,but most of them are tested within a small current density range,typically no more than 500 mA cm^(-2).To realize the industrial application of hydrogen production from water electrolysis,it is essential to develop high-efficiency HER electrocatalysts at high current density(HCD≥500 mA cm^(-2)).Nevertheless,it remains challenging and significant to rational design HCD electrocatalysts for HER.In this paper,the design strategy of HCD electrocatalysts is discussed,and some HCD electrocatalysts for HER are reviewed in seven categories(alloy,metal oxide,metal hydroxide,metal sulfide/selenide,metal nitride,metal phosphide and other derived electrocatalysts).At the end of this article,we also pro-pose some viewpoints and prospects for the future development and research directions of HCD electrocatalysts for HER.
基金Project(2009AA050702)supported by the National High-tech Research and Development Program of ChinaProject(GC06A212)supported by the Scientific Technology Project of Heilongjiang Province,China+2 种基金Project(50871033)supported by the National Natural Science Foundation of ChinaProject(208181)supported by the Key Project of Ministry of Education,ChinaProject(HEUCF101002)supported by the Fundamental Research Funds for the Central Universities,China
文摘Mg-Li-Gd alloys were prepared by electrochemical codeposition from LiCl-KCl-MgCl 2 -Gd 2 O 3 melts on molybdenum electrode with constant current density at 823 and 973 K. The microstructure of the Mg-Li-Gd alloys was analyzed by X-ray diffraction （XRD）, optical microscopy （OM） and scanning electron microscopy （SEM）. The results show that magnesium and gadolinium deposit mainly in the first 30 min, and the alloy obtained contains 96.53% Mg, 0.27% Li and 3.20% Gd （mass fraction）. Then, the reduction of lithium ions occurs quickly. The composition of alloy can be adjusted by controlling electrolysis time or Gd 2 O 3 concentration in LiCl-KCl melts. With the addition of Gd into Mg-Li alloys, the corrosion resistance of the alloys is enhanced. XRD results suggest that Mg 3 Gd and Mg 2 Gd can be formed in Mg-Li-Gd alloys. The distribution of Gd element in Mg-Li-Gd alloys indicates that Gd element mainly distributes at the grain boundaries of Mg-Li-Gd alloys.
基金Projects(2012BAE01B04)supported by the National Key and Technology R&D Program of ChinaProject(KZCX2-XB3-06)supported by Western Action Program,Chinese Academy of Sciences
文摘Mg-La alloys were prepared by constant voltage electrolysis in the molten salt system of MgC12-LaC13-KC1 at 750℃, with a graphite crucible as the anode and a tungsten rod as the cathode. The effect of oxide and fluoride addition on the electrolysis was investigated comprehensively. X-ray diffraction （XRD） was used to characterize some of the Mg-La alloy products and the sludges. As the content of MgO or La203 in the electrolyte increased, both the current efficiency and the mass of alloy product decreased, indicating that both MgO and La203 may take part in the reactions in the electrolyte. When the same mass of the oxide was added, compared with La203, MgO had a more pronounced effect on both the current efficiency and the mass of alloy product. XRD studies confirmed the formation of LaOC1 when MgO or LazO3 was added into the electrolyte. The formation of LaOCl sludge would be the main reason for the negative effect of the oxide addition on both the current efficiency and the mass of alloy. In the electrolytic system, the addition of CaF2 was not helpful to suppress the negative effect of MgO on the electrolysis, probably due to the complex reactions of the La compounds in the electrolyte.
基金Projects(51104042,51074046)supported by the National Natural Science Foundation of ChinaProject(N120405006)supported by the Fundamental Research Funds for the Central University,China
文摘Extracting aluminum from aluminum alloys in AlCl3-NaCl molten salts was investigated. Al coating was deposited on the copper cathode by the method of direct current deposition using aluminum alloys as anode. The purity of the deposited aluminum is about 99.7% with the energy consumption of 3-9 kW＆#183;h per kg Al, and the current efficiency is 44%-64% when the deposition process is carried out under 100 mA/cm2 for 4 h at 170 ＆#176;C. The effects of experimental parameters, such as molar ratio of AlCl3 to NaCl, cathodic current density and electrolysis time, on the current efficiency were studied. The molar ratio of AlCl3 to NaCl has little effect on the current efficiency, and the increase of deposition temperature is beneficial to the increase of current efficiency. However, the increase of current density or electrolysis time results in the decrease of current efficiency. The decrease of current efficiency is mainly related to the formation of dendritic or powder deposit of aluminum which is easy to fall into the electrolyte.
基金Project supported by the Fundamental Research Funds for the Central Universities of China
文摘Mg-Al-Sn alloy is one of the new developed anode materials for seawater activated batteries. The potentiodynamic polarization, galvanostatic discharge and electrochemical impedance spectroscopy of Mg-6%Al-1%Sn and Mg-6%Al-5%Sn(mass fraction) alloys in seawater were studied and compared with the commercial AZ31 and AP65 alloys. The results show that the Mg-6%Al-1%Sn alloy obtains the most negative discharge potential of average-1.611V with a electric current density of 100 mA/cm2. EIS studies reveal that the Mg-Al-Sn alloy/seawater interfacial electrochemical process is determined by an activation controlled reaction. The assembled prototype batteries with Mg-6%Al-1%Sn alloy as anodes and Ag Cl as cathodes exhibit a satisfactory integrated discharge properties.
文摘The electrochemical synthesis silicon wires by electrorefining metallurgical grade silicon in thermally dried and pre-electrolyzed molten KF-NaF eutectic were studied at temperatures 800-900 ℃ using cyclic voltammetry and ac impedance. One oxidation peak at -0.14 V could be attributed to the reaction of Si to Si4＋. A cathodic peak occurred at -0.56 V in the cyclic voltammogram and one response semicircle in the ac impedance spectrum was observed, supporting a one-step electrochemical reduction process of Si4＋-→Si. The electrochemical reaction of silicon was controlled by the diffusion process. The purity of electrorefined silicon wires was up to 99.999% by ICP-MS analysis.
基金Project(2011AA061003)supported by the National High-Tech Research and Development Program of China
文摘The physical and mathematical model of an operating electrowinning cell was established, and the flow of electrolyte was numerically simulated by the commercial software Fluent. The results indicate that there are two circulations at the surface flow where part of electrolyte backflows to the inlet from the side of cell, and the rest flows directly to the outlet, and the separation of two circulations with opposite direction occurs at the 20th pair of anode-cathode. This phenomenon was observed in the real operation. The electrolyte flows into the space between anode and cathode from the side portion of the cell. Meanwhile, the interelectrode effective flow rate （IEFR） is put forward to describe quantitively the flow field characteristics and is defined as the ratio of electrolyte flow between the anode and cathode to the total flow area. The influences of structure parameters and operating conditions on IEFR, such as the inlet angle, the volumetric flow rate, the inlet position and the height of steel baffles were simulated. The inlet position has a significant influence on the IEFR and its optimal value is 0.9 m below free surface. The inlet angle should be in the range from -10° to 10°. IEFR is in linear proportion with the volumetric flow rate, and the height of the steel baffle has little influence on the flow field.
基金EPSRC for financial support through the LATEST2 Programme grant (EP/H020047/1)
文摘The corrosion pathways in AA2024-T3, AA5083-O and AA6082-T6 alloys have been investigated. The objective of the investigation is to further the understanding of the complex localised corrosion mechanism in aluminium alloys. The investigation was carried out by examining the corroded surfaces of the alloys after potentiodynamic polarization tests in a 3.5% NaCl solution with the aid of a scanning electron microscope, and by analysing the flow of anolyte solution using the scanning vibrating electrode technique. The results revealed that the overall corrosion pathways in the alloys are distinctively different and are influenced by the flow of anolyte solution. Also revealed, was the fact that corrosion propagates in two ways （particularly in the AA5083-O and AA6082-T6 alloys）： an overall pathway in the corrosion front （filiform-like pathway in the AA5083 alloy and organized linear pathways in AA6082 alloy）; and the crystallographic channelling along the （100） directions. These are dependent on the grain distinct features of the AA5083-O and AA6082-T6 alloys and are not influenced by the presence of coarse second phase particles in these alloys, compared with the AA2024-T3 alloy, where the corrosion pathways are more dependent on the presence of second phase particles and grain boundary character.
