The corrosion resistance of 2024-T3 aluminum alloy was improved by anodizing treatment in a mixed electrolyte containing 10% sulfuric acid, 5% boric acid and 2% phosphoric acid. Electrochemical impedance spectroscopy ...The corrosion resistance of 2024-T3 aluminum alloy was improved by anodizing treatment in a mixed electrolyte containing 10% sulfuric acid, 5% boric acid and 2% phosphoric acid. Electrochemical impedance spectroscopy （EIS） technique was used to study the corrosion behavior of the anodized alloy. Using Tafel plot and salt spray techniques, it is revealed that the anodizing treatment of 2024-T3 aluminum alloy in sulfuric-boric-phosphoric acids provides better corrosion resistance and durability in comparison with the anodizing treatment in phosphoric acid or sulfuric-boric acids. This electrolyte can be a suitable alternative for chromate baths which are generally used in the anodizing of aluminum alloys.展开更多
Investigations have revealed the permeation performance of electrolytes in the separation process by nanofiltration membranes in single salt solutions. However, there is still not much information about the separation...Investigations have revealed the permeation performance of electrolytes in the separation process by nanofiltration membranes in single salt solutions. However, there is still not much information about the separation process of mixed electrolyte solutions, and by now most of the investigations have been on solutions containing three kinds of ions, in which anions are mostly NO-3, Cl- and SO 2-4, and cations are mostly Na+,Ca 2+ and Mg 2+. In this work, permeation experiments of three kinds of nanofiltration membranes（ESNA 1-LF, ESNA 1 and LES 90） for binary electrolyte solutions（NaNO3, Ca（NO3）2; NaCl, NaNO3; NaCl, Ca（NO3）2; etc.） were carried out, and the interactions between co-ions and counter-ions were investigated.The result showed that the ion with better permeation performance would permeate first,thus depressing the rejection of itself and enhancing the rejection of the co-ion with poor permeation performance. Interaction between co-ions with similar permeation performance was not obvious. Counter-ions influenced each other mainly through the electroneutrality principle.展开更多
The anodizing oxidation process on 2024 aluminum alloy was researched in the mixed electrolyte with the composition of 30 g/L boric acid, 2 g/L sulfosalicylic acid and 8 g/L phosphate. The results reveal that the pre-...The anodizing oxidation process on 2024 aluminum alloy was researched in the mixed electrolyte with the composition of 30 g/L boric acid, 2 g/L sulfosalicylic acid and 8 g/L phosphate. The results reveal that the pre-treatment and the composition of the mixed electrolyte have influence on the properties of the films and the anodizing oxidation process. Under the condition of controlled potential, the anodizing oxidation current—time response curve displays "saddle" shape. First, the current density reaches a peak value of 8-20 A/dm2 and then decreases rapidly, finally maintains at 1-2 A/dm2. The film prepared in the mixed electrolyte is of porous-type with 20 nm in pore size and 500 μm-2 in porosity. Compared with the conventional anodic film obtained in sulfuric acid, the pore wall of the porous layer prepared in this work is not continuous, which seems to be deposited by small spherical grains. This porous structure of the anodic film may result from the characteristics of the mixed electrolyte and the special anodizing oxidation process. The surface analysis displays that the anodic film is amorphous and composed of O, Al, C, P, S, Si and no copper element is detected.展开更多
Lithium-sulfur(Li-S) battery is considered as a promising energy storage system to realize high energy density.Nevertheless,unstable lithium metal anode emerges as the bottleneck toward practical applications,especial...Lithium-sulfur(Li-S) battery is considered as a promising energy storage system to realize high energy density.Nevertheless,unstable lithium metal anode emerges as the bottleneck toward practical applications,especially with limited anode excess required in a working full cell.In this contribution,a mixed diisopropyl ether-based(mixed-DIPE) electrolyte was proposed to effectively protect lithium metal anode in Li-S batteries with sulfurized polyacrylonitrile(SPAN) cathodes.The mixed-DIPE electrolyte improves the compatibility to lithium metal and suppresses the dissolution of lithium polysulfides,rendering significantly improved cycling stability.Concretely,Li | Cu half-cells with the mixed-DIPE electrolyte cycled stably for 120 cycles,which is nearly five times longer than that with routine carbonate-based electrolyte.Moreover,the mixedDIPE electrolyte contributed to a doubled life span of 156 cycles at 0.5 C in Li | SPAN full cells with ultrathin 50 μm Li metal anodes compared with the routine electrolyte.This contribution affords an effective electrolyte formula for Li metal anode protection and is expected to propel the practical applications of high-energy-density Li-S batteries.展开更多
Proton exchange membrane(PEM)water electrolysis represents a promising technology for green hydrogen production,but its widespread deployment is greatly hindered by the indispensable usage of platinum group metal cata...Proton exchange membrane(PEM)water electrolysis represents a promising technology for green hydrogen production,but its widespread deployment is greatly hindered by the indispensable usage of platinum group metal catalysts,especially iridium(Ir)based materials for the energy-demanding oxygen evolution reaction(OER).Herein,we report a new sequential precipitation approach to the synthesis of mixed Ir-nickel(Ni)oxy-hydroxide supported on antimony-doped tin oxide(ATO)nanoparticles(IrNiyO_(x)/ATO,20 wt.%(Ir+Ni),y=0,1,2,and 3),aiming to reduce the utilisation of scarce and precious Ir while maintaining its good acidic OER performance.When tested in strongly acidic electrolyte(0.1 M HClO_(4)),the optimised IrNi1Ox/ATO shows a mass activity of 1.0 mAµgIr^(−1) and a large turnover frequency of 123 s^(−1) at an overpotential of 350 mV,as well as a comparatively small Tafel slope of 50 mV dec^(−1),better than the IrOx/ATO control,particularly with a markedly reduced Ir loading of only 19.7µgIr cm^(−2).Importantly,IrNi1O_(x)/ATO also exhibits substantially better catalytic stability than other reference catalysts,able to continuously catalyse acidic OER at 10 mA cm^(−2) for 15 h without obvious degradation.Our in-situ synchrotron-based x-ray absorption spectroscopy confirmed that the Ir^(3+)/Ir^(4+)species are the active sites for the acidic OER.Furthermore,the performance of IrNi1Ox/ATO was also preliminarily evaluated in a membrane electrode assembly,which shows better activity and stability than other reference catalysts.The IrNi1Ox/ATO reported in this work is a promising alternative to commercial IrO_(2) based catalysts for PEM electrolysis.展开更多
Herein, the influence of the concentration design and comprehensive performance of the sulfate-phosphoric mixed acid system electrolyte is investigated to realize an electrolyte that maintains high energy density and ...Herein, the influence of the concentration design and comprehensive performance of the sulfate-phosphoric mixed acid system electrolyte is investigated to realize an electrolyte that maintains high energy density and stable operation at high temperatures. Static stability tests have shown that VOPO4 precipitation occurs only with vanadium(V) electrolyte. The concentration of vanadium ion of 2.0–2.2 mol·L^(–1), phosphoric acid of 0.10–0.15 mol·L^(–1), and sulfuric acid of 2.5–3.0 mol·L^(–1) are suitable for a vanadium redox flow battery in the temperature range from –20 to 50 ℃. The equations for predicting the viscosity and conductivity of electrolytes are obtained by the response surface method. The optimized electrolyte overcomes precipitation generation. It has 2.8 times higher energy density than the non-phosphate electrolyte, and a coulomb efficiency of 94.0% at 50 ℃. The sulfate-phosphoric mixed acid system electrolyte promotes the electrode reaction process, increases the current density, and reduces the resistance. This work systematically optimizes the concentrations of composition of positive and negative vanadium electrolytes with mixed sulfate-phosphoric acid. It provides a basis for the different valence states and comprehensive properties of sulfate-phosphoric mixed acid system vanadium electrolytes under extreme environments, guiding engineering applications.展开更多
Ionic partition equilibrium on a charged membrane immersed in a mixed electrolyte solution was systematically investigated and several models were established for the determination of partition coefficients. On the ba...Ionic partition equilibrium on a charged membrane immersed in a mixed electrolyte solution was systematically investigated and several models were established for the determination of partition coefficients. On the basis of theoretical models, the effects of the concentration ratio λ of the fixed group(charged density) to reference electrolyte, the concentration ratio η between the two electrolytes existing in the solution and the valence of the electrolyte ions on the partition equilibrium in a positively charged membrane were analyzed and simulated within the chosen parameters in detail. The obtainable results can also be applicable to a sytem of mixed electrolytes contacting with a negatively charged membrane. The theoretical calculations were confirmed with the experimental data of model mixed electrolytes, NaCl+HCl and CaCl 2+NaCl partitioned in the system of self made negatively charged membrane sulphonated poly(phenylene oxide)(SPPO) with different charge densities.展开更多
The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inade...The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inadequate ionic/electronic conduction network between the S(or Li_(2)S),conductive carbon,and solid-state electrolytes(SSEs)for achieving a swift(dis)charge reaction.Herein,a series of hybrid ionic/electronic conduction triple-phase interfaces with transition metal and nitrogen co-doping were designed.The graphitic ordered mesoporous carbon frameworks(TM-N-OMCs;TM=Fe,Co,Ni,and Cu)serve as hosts for Li_(2)S and Li_(6)PS_(5)Cl(LPSC)and provide abundant reaction sites on the triple interface.Results from both experimental and computational research display that the combination of Cu-N co-dopants can promote the Li-ion diffusion for rapid transformation of Li_(2)S with adequate ionic(6.73×10^(−4)S·cm^(−1))/electronic conductivities(1.77×10^(−2)S·cm^(−1))at 25℃.The as-acquired Li_(2)S/Cu-N-OMC/LPSC electrode exhibits a high reversible capacity(1147.7 mAh·g^(−1))at 0.1 C,excellent capacity retention(99.5%)after 500 cycles at 0.5 C,and high areal capacity(7.08 mAh·cm^(−2)).展开更多
制备了可充镁电池电解质苯酚基镁盐,以四氢呋喃(THF)与N-甲基-N-丁基-哌啶-双三氟甲基磺酰胺(PP14TFSI)离子液体混合物代替四氢呋喃作为该电解质的溶剂.当THF与PP14TFSI体积配比为1:1时,该苯酚基镁盐电解液镁可逆溶出性能最佳,电化学窗...制备了可充镁电池电解质苯酚基镁盐,以四氢呋喃(THF)与N-甲基-N-丁基-哌啶-双三氟甲基磺酰胺(PP14TFSI)离子液体混合物代替四氢呋喃作为该电解质的溶剂.当THF与PP14TFSI体积配比为1:1时,该苯酚基镁盐电解液镁可逆溶出性能最佳,电化学窗口宽(2.7 V vs.Mg),离子电导率高(7.77 mS·cm-1).此外,热重测试表明离子液体的加入大大降低了THF溶剂的挥发性,提高了可充镁电池的安全性能.四氢呋喃+N-甲基-N-丁基-哌啶-双三氟甲基磺酰胺混合溶剂有望作为可充镁电池电解液的首选溶剂.展开更多
文摘The corrosion resistance of 2024-T3 aluminum alloy was improved by anodizing treatment in a mixed electrolyte containing 10% sulfuric acid, 5% boric acid and 2% phosphoric acid. Electrochemical impedance spectroscopy （EIS） technique was used to study the corrosion behavior of the anodized alloy. Using Tafel plot and salt spray techniques, it is revealed that the anodizing treatment of 2024-T3 aluminum alloy in sulfuric-boric-phosphoric acids provides better corrosion resistance and durability in comparison with the anodizing treatment in phosphoric acid or sulfuric-boric acids. This electrolyte can be a suitable alternative for chromate baths which are generally used in the anodizing of aluminum alloys.
文摘Investigations have revealed the permeation performance of electrolytes in the separation process by nanofiltration membranes in single salt solutions. However, there is still not much information about the separation process of mixed electrolyte solutions, and by now most of the investigations have been on solutions containing three kinds of ions, in which anions are mostly NO-3, Cl- and SO 2-4, and cations are mostly Na+,Ca 2+ and Mg 2+. In this work, permeation experiments of three kinds of nanofiltration membranes（ESNA 1-LF, ESNA 1 and LES 90） for binary electrolyte solutions（NaNO3, Ca（NO3）2; NaCl, NaNO3; NaCl, Ca（NO3）2; etc.） were carried out, and the interactions between co-ions and counter-ions were investigated.The result showed that the ion with better permeation performance would permeate first,thus depressing the rejection of itself and enhancing the rejection of the co-ion with poor permeation performance. Interaction between co-ions with similar permeation performance was not obvious. Counter-ions influenced each other mainly through the electroneutrality principle.
基金Project(06JJ4005) supported by the Natural Science Foundation of Hunan Province, China
文摘The anodizing oxidation process on 2024 aluminum alloy was researched in the mixed electrolyte with the composition of 30 g/L boric acid, 2 g/L sulfosalicylic acid and 8 g/L phosphate. The results reveal that the pre-treatment and the composition of the mixed electrolyte have influence on the properties of the films and the anodizing oxidation process. Under the condition of controlled potential, the anodizing oxidation current—time response curve displays "saddle" shape. First, the current density reaches a peak value of 8-20 A/dm2 and then decreases rapidly, finally maintains at 1-2 A/dm2. The film prepared in the mixed electrolyte is of porous-type with 20 nm in pore size and 500 μm-2 in porosity. Compared with the conventional anodic film obtained in sulfuric acid, the pore wall of the porous layer prepared in this work is not continuous, which seems to be deposited by small spherical grains. This porous structure of the anodic film may result from the characteristics of the mixed electrolyte and the special anodizing oxidation process. The surface analysis displays that the anodic film is amorphous and composed of O, Al, C, P, S, Si and no copper element is detected.
基金supported by National Key Research and Development Program(2016YFA0202500 and 2016YFA0200102)National Natural Science Foundation of China(21776019,21825501,and U1801257)the Tsinghua University Initiative Scientific Research Program
文摘Lithium-sulfur(Li-S) battery is considered as a promising energy storage system to realize high energy density.Nevertheless,unstable lithium metal anode emerges as the bottleneck toward practical applications,especially with limited anode excess required in a working full cell.In this contribution,a mixed diisopropyl ether-based(mixed-DIPE) electrolyte was proposed to effectively protect lithium metal anode in Li-S batteries with sulfurized polyacrylonitrile(SPAN) cathodes.The mixed-DIPE electrolyte improves the compatibility to lithium metal and suppresses the dissolution of lithium polysulfides,rendering significantly improved cycling stability.Concretely,Li | Cu half-cells with the mixed-DIPE electrolyte cycled stably for 120 cycles,which is nearly five times longer than that with routine carbonate-based electrolyte.Moreover,the mixedDIPE electrolyte contributed to a doubled life span of 156 cycles at 0.5 C in Li | SPAN full cells with ultrathin 50 μm Li metal anodes compared with the routine electrolyte.This contribution affords an effective electrolyte formula for Li metal anode protection and is expected to propel the practical applications of high-energy-density Li-S batteries.
基金supported by the National Innovation Agency of Portugal through the project Baterias 2030(Grant No.POCI-01-0247-FEDER-046109)J R E would like to acknowledge the Fundación General CSIC’s ComFuturo programme which has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No.101034263+2 种基金The authors appreciate Dr Laura Simonelli and Dr Vlad Martin Diaconescu for their assistance in XAS measurements at the beamline BL22-CLÆSS,ALBA synchrotron(experiment AV-2022025706)R M is grateful to the Portuguese Foundation for Science and Technology(FCT)for the doctoral grant(Grant No.2021.06496.BD)R M and A M are grateful for the financial support from:LA/P/0045/2020,UIDB/00511/2020 and UIDP/00511/2020,funded by the national funds through FCT/MCTES(PIDDAC)。
文摘Proton exchange membrane(PEM)water electrolysis represents a promising technology for green hydrogen production,but its widespread deployment is greatly hindered by the indispensable usage of platinum group metal catalysts,especially iridium(Ir)based materials for the energy-demanding oxygen evolution reaction(OER).Herein,we report a new sequential precipitation approach to the synthesis of mixed Ir-nickel(Ni)oxy-hydroxide supported on antimony-doped tin oxide(ATO)nanoparticles(IrNiyO_(x)/ATO,20 wt.%(Ir+Ni),y=0,1,2,and 3),aiming to reduce the utilisation of scarce and precious Ir while maintaining its good acidic OER performance.When tested in strongly acidic electrolyte(0.1 M HClO_(4)),the optimised IrNi1Ox/ATO shows a mass activity of 1.0 mAµgIr^(−1) and a large turnover frequency of 123 s^(−1) at an overpotential of 350 mV,as well as a comparatively small Tafel slope of 50 mV dec^(−1),better than the IrOx/ATO control,particularly with a markedly reduced Ir loading of only 19.7µgIr cm^(−2).Importantly,IrNi1O_(x)/ATO also exhibits substantially better catalytic stability than other reference catalysts,able to continuously catalyse acidic OER at 10 mA cm^(−2) for 15 h without obvious degradation.Our in-situ synchrotron-based x-ray absorption spectroscopy confirmed that the Ir^(3+)/Ir^(4+)species are the active sites for the acidic OER.Furthermore,the performance of IrNi1Ox/ATO was also preliminarily evaluated in a membrane electrode assembly,which shows better activity and stability than other reference catalysts.The IrNi1Ox/ATO reported in this work is a promising alternative to commercial IrO_(2) based catalysts for PEM electrolysis.
基金supported by the National Natural Science Foundation of China(Grant No.51774216)Hubei Technical Innovation Special Project of China(Grant No.2017ACA185)Science and technology innovation Talent program of Hubei Province(Grant No.2022EJD002).
文摘Herein, the influence of the concentration design and comprehensive performance of the sulfate-phosphoric mixed acid system electrolyte is investigated to realize an electrolyte that maintains high energy density and stable operation at high temperatures. Static stability tests have shown that VOPO4 precipitation occurs only with vanadium(V) electrolyte. The concentration of vanadium ion of 2.0–2.2 mol·L^(–1), phosphoric acid of 0.10–0.15 mol·L^(–1), and sulfuric acid of 2.5–3.0 mol·L^(–1) are suitable for a vanadium redox flow battery in the temperature range from –20 to 50 ℃. The equations for predicting the viscosity and conductivity of electrolytes are obtained by the response surface method. The optimized electrolyte overcomes precipitation generation. It has 2.8 times higher energy density than the non-phosphate electrolyte, and a coulomb efficiency of 94.0% at 50 ℃. The sulfate-phosphoric mixed acid system electrolyte promotes the electrode reaction process, increases the current density, and reduces the resistance. This work systematically optimizes the concentrations of composition of positive and negative vanadium electrolytes with mixed sulfate-phosphoric acid. It provides a basis for the different valence states and comprehensive properties of sulfate-phosphoric mixed acid system vanadium electrolytes under extreme environments, guiding engineering applications.
基金Supported by the National Natural Science Foundation of China(No.2 0 10 6 0 15 and2 9976 0 4 0 ) Natural Science Foun-dation of Anhui Province(No.990 4 5 4 31) and Key Foundation of Educational Comm ittee of Anhui Province(No.2 0 0 0 jl2 5 5 zd)
文摘Ionic partition equilibrium on a charged membrane immersed in a mixed electrolyte solution was systematically investigated and several models were established for the determination of partition coefficients. On the basis of theoretical models, the effects of the concentration ratio λ of the fixed group(charged density) to reference electrolyte, the concentration ratio η between the two electrolytes existing in the solution and the valence of the electrolyte ions on the partition equilibrium in a positively charged membrane were analyzed and simulated within the chosen parameters in detail. The obtainable results can also be applicable to a sytem of mixed electrolytes contacting with a negatively charged membrane. The theoretical calculations were confirmed with the experimental data of model mixed electrolytes, NaCl+HCl and CaCl 2+NaCl partitioned in the system of self made negatively charged membrane sulphonated poly(phenylene oxide)(SPPO) with different charge densities.
基金supported by the National Natural Science Foundation of China(No.T2241003)the National Key Research and Development Program of China(No.2022YFB4003500)the Key R&D project of Hubei Province,China(No.2021AAA006).
文摘The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inadequate ionic/electronic conduction network between the S(or Li_(2)S),conductive carbon,and solid-state electrolytes(SSEs)for achieving a swift(dis)charge reaction.Herein,a series of hybrid ionic/electronic conduction triple-phase interfaces with transition metal and nitrogen co-doping were designed.The graphitic ordered mesoporous carbon frameworks(TM-N-OMCs;TM=Fe,Co,Ni,and Cu)serve as hosts for Li_(2)S and Li_(6)PS_(5)Cl(LPSC)and provide abundant reaction sites on the triple interface.Results from both experimental and computational research display that the combination of Cu-N co-dopants can promote the Li-ion diffusion for rapid transformation of Li_(2)S with adequate ionic(6.73×10^(−4)S·cm^(−1))/electronic conductivities(1.77×10^(−2)S·cm^(−1))at 25℃.The as-acquired Li_(2)S/Cu-N-OMC/LPSC electrode exhibits a high reversible capacity(1147.7 mAh·g^(−1))at 0.1 C,excellent capacity retention(99.5%)after 500 cycles at 0.5 C,and high areal capacity(7.08 mAh·cm^(−2)).
文摘制备了可充镁电池电解质苯酚基镁盐,以四氢呋喃(THF)与N-甲基-N-丁基-哌啶-双三氟甲基磺酰胺(PP14TFSI)离子液体混合物代替四氢呋喃作为该电解质的溶剂.当THF与PP14TFSI体积配比为1:1时,该苯酚基镁盐电解液镁可逆溶出性能最佳,电化学窗口宽(2.7 V vs.Mg),离子电导率高(7.77 mS·cm-1).此外,热重测试表明离子液体的加入大大降低了THF溶剂的挥发性,提高了可充镁电池的安全性能.四氢呋喃+N-甲基-N-丁基-哌啶-双三氟甲基磺酰胺混合溶剂有望作为可充镁电池电解液的首选溶剂.
