CN104319408A - Silver copper nano alloy air electrode catalyst layer and deposition method thereof - Google Patents

Silver copper nano alloy air electrode catalyst layer and deposition method thereof Download PDF

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CN104319408A
CN104319408A CN201410542528.1A CN201410542528A CN104319408A CN 104319408 A CN104319408 A CN 104319408A CN 201410542528 A CN201410542528 A CN 201410542528A CN 104319408 A CN104319408 A CN 104319408A
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electrode
catalyst layer
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copper nano
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CN104319408B (en
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陈福义
吴小强
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Northwestern Polytechnical University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention relates to a silver copper nano alloy air electrode catalyst and a deposition method thereof. The silver copper nano alloy air electrode catalyst layer is in a film shape and consists of 50 to 90 percent of Ag and 10 to 50 percent of Cu, wherein the percentage is the atomic percentage. The silver copper nano alloy is directly deposited onto a foam nickel current collector electrode by adopting a pulse laser deposition method, a silver copper single-phase solid solution alloying cathode catalyst layer is prepared to form a catalytic layer which does not contain carbon and contains Teflon. The micro tissue of the silver copper nano alloy air electrode catalyst layer is formed by dispersing silver copper nano alloy particles in a copper amorphous substrate, the average nano particle granularity is 2.5nm to 2.8nm, and the distribution granularity is 1nm to 5nm. The open-circuit voltage of the silver copper nano alloy film in a primary zinc-air battery is 1.42V to 1.44V, the power density can reach up to 86.3mW.cm<-2> and is improved by 20 percent, and the charging-discharging circulating efficiency in a secondary zinc-air battery is more than 41 percent.

Description

Silver-copper nano alloy air-electrode catalyst layer and deposition process thereof
Technical field
The invention belongs to rechargeable metal and regeneratable fuel cell field, catalyst layer specifically in above-mentioned battery, oxygen electrode and air electrode used and preparation method thereof.
Background technology
In recent years, due to energy environment crisis, traditional old and useless battery is large to the pollution of environment, and regenerative resource is as photovoltaic, and wind energy etc. exist intermittent problems and make Development of Novel renewable energy device become the focus of energy field research.Under field conditions (factors), metal-air cell and fuel cell oxidized metal or fuel can produce electronics on anode, reduce oxygen on cathode catalyst layer simultaneously, produce hydroxide ion or water, and are electric energy by chemical energy.Because anode metal or oxidized are spontaneous processes, therefore on air cell, the catalytic efficiency of the oxygen reduction reaction of catalyst layer is the key affecting battery performance.Whole reaction is spontaneous energy that need not be extra in above process, and what cathode reaction simultaneously consumed is oxygen, generation be pollution-free, sustainable to environment of water or hydroxyl, there is the ability fully solving current energy environment issues.Current cathod catalyst mainly uses Pt/C as catalyst, but metal platinum is expensive and scarcity of resources, constraining the commercial applications that Pt is catalyst based. argent price only has 1/50th of Pt, in alkaline solution, have the oxygen reduction reaction electrocatalytic properties not worse than platinum, silver and silver-base alloy have started to be used as air electrode catalyst at present.
In recent years, Nanjing University Han etc. is devoted to the research of silver and silver-base alloy, deliver " Synthesis of Octopus-Tentacle-Like Cu Nanowire-Ag Nanocrystals Heterostructures and their Enhanced Electrocatalytic Performance for Oxygen Reduction Reaction " at ACS Appl.Mater.Interfaces, this article to be synthesized bimetallic Ag-Cu nanostructure by solution reduction, XRD analysis shows that in nanostructure, Ag and Cu is a point phase segregation, demonstrate the ORR catalytic activity of Ag-Cu nano-catalytic layer higher than Ag/C.At present, the research for money base nano-alloy cathode catalyst layer and preparation method thereof has achieved certain achievement.Northwestern Polytechnical University is disclose a kind of fuel cell silver-copper nano alloy negative electrode and preparation method thereof in the patent of invention of ZL201110051634.6 in the patent No., the method has been synthesized by electrochemical deposition method and has been had silver-colored face-centred cubic structure silver-copper nano dendrite, in alkaline electrolyte, experimental studies have found that silver-bearing copper bimetal nano alloy is to H 2o 2there is oxygen reduction reaction catalytic property, the air electrode catalyst of fuel cell can be used as. US Patent No. 8685575B2 discloses a kind of catalyst layer component of fuel battery air electrode, active component is Ag and CoTMPP, carbon containing 50-80%, containing Teflon 2-20%, under the operating condition of circulation alkaline electrolyte and zinc raw material, monocell can at 280mA/cm 2condition under, reach 1 volt of voltage.Be the 200620004676.9 empty metal fuel battery oxygen electrodes of zinc reporting that a kind of heat seal process method makes at application number.Afflux is nickel foam very, and catalyst layer is by silver, and copper, the nitrates decompose of manganese etc. forms, and carbon containing is 50-94%, containing Teflon 10-30%, is rolled into the film of 0.1-0.2 millimeter.Northwestern Polytechnical University is by controlling alloy composition to modulate this alloy surface plasmon resonant frequency in patent No. CN102321825A, and along with the increase of silver content ratio in yellow gold, red shift appears in alloy plasma absworption peak.The silver-copper nano dendrite formed has coarse, clean surface and large specific area, in Surface-enhanced spectroscopic, the catalysis of surface plasma optics and surface plasma enhancing solar absorption etc., have good application.Northwestern Polytechnical University uses electrochemical deposition method to prepare copper silver nanoparticle alloy catalyst at patent No. CN102157740A, and it can be used as the cathod catalyst of sodium borohydride/using hydrogen peroxide as fuel battery, effectively reduce the application cost of sodium borohydride/using hydrogen peroxide as fuel cell cathode eelctro-catalyst, and excellent catalytic effect.
Although silver and silver-base alloy have had preliminary experiment as air electrode catalyst, its catalytic activity and durability can not meet the commercial requirements of extensive use.Existing air electrode cathod catalyst technology of preparing is in catalyst component, preparation technology and there is following key issue with the carrier use of this catalyst layer:
(1) on air electrode catalyst composition, in current document the silver element of silver-base alloy catalyst not and copper, manganese these can make to be conducive to Ag alloying, form the transition metal of stably catalyzed oxidant layer.Meanwhile, the d orbit centre saturation of fine silver is lower, and weak to the absorption of oxygen, oxygen reduction reaction catalytic activity is more weak, and the suitable metallic element of silver needs adulterates and develops new silver-base alloy nanocatalyst, improves its catalytic activity.
(2) in air-electrode catalyst layer preparation technology, in current document, the synthesis of silver alloy eelctro-catalyst relates to manual operations and solution process, not there is the characteristic making to prepare cell process automation, technique is restive simultaneously, be unfavorable for parameter setting module, the energy density that the eelctro-catalyst of laboratory stage application preparation and prototype battery thereof may reach and cycle life, expectability does not realize in yield production type battery.
(3) on air-electrode catalyst layer carrier, current silver-base alloy uses various forms of carbon (as acetylene black and electrically conductive graphite) to do catalyst carrier in a large number, when air cell charges, air electrode afflux very nickel foam can produce oxygen, the carbon of nascent state oxygen meeting strong corrosion air electrode, cause Ag base catalytic active component to come off, through use after a while, the catalytic activity of air electrode can significantly reduce.
Summary of the invention
For overcoming the unstable properties of the air electrode existed in prior art, being unsuitable for the deficiency of automated production, the present invention proposes a kind of silver-copper nano alloy air-electrode catalyst layer and deposition process thereof.
Described silver-copper nano alloy air-electrode catalyst layer is film-form, is made up of 50 ~ 90%Ag and 10 ~ 50%Cu, and described percentage is atomic percent.
The microstructure of described silver-copper nano alloy air-electrode catalyst layer be silver-copper nano alloy particle dispersion in the noncrystal substrate of copper, average nanoparticle particle diameter position 2.5 ~ 2.8nm, distribution particle diameter is between 1 ~ 5nm.
Preparing described silver-copper nano alloy air-electrode catalyst layer detailed process is:
Step 1, process nickel foam substrate.
Step 2, pulsed laser deposition yellow gold nanocatalyst.Being fixed on the sample stage of impulse laser deposition system by the nickel foam substrate cleaned up, is that the yellow gold target of 5 ~ 9:5 ~ 1 is fixed on rotary target platform by atomic ratio, and wherein yellow gold target is the yellow gold of the smelting process die casting that market is bought.The distance regulating substrate and target is 5cm.Open vacuum system, vacuum degree in vacuum chamber is extracted into 2.0*10 -4pa, makes target and substrate with the rotating speed uniform rotation of 5r/min.Block sample stage with baffle plate, unbalanced pulse laser, laser ablation target 2min is to remove target material surface oxide.Take off baffle plate, the pulse duration arranging LASER Light Source is 6ns, and laser repetition rate is 10Hz, pulsed laser deposition 45 ~ 120min, under the condition of continuous vacuum, drops to room temperature by sample, in vacuum chamber, be filled with nitrogen take out sample, obtain yellow gold nano-catalytic oxidant layer.
Step 3, preparation air diffusion layer.Acetylene black mixes in the ratio of 1:2 ~ 3 with PTFE by the preparation method of air diffusion layer in absolute ethyl alcohol, ultrasonic disperse 15min, and magnetic rotor stirs 30min, obtains the mixture of acetylene black and PTFE.The mixture that the thermostat water bath mixture of acetylene black and PTFE being placed in 80 ~ 90 DEG C is incubated to described acetylene black and PTFE forms paste body shape, with roll squeezer, the mixture of the paste body shape acetylene black obtained and PTFE is pressed into the membranaceous air diffusion layer that thickness is 0.5 ~ 0.8mm.
Step 4, assembling zinc and air cell.The yellow gold nanocatalyst obtained is placed on air diffusion layer surface, with roll squeezer, catalyst layer and air diffusion layer is pressed into the membranaceous air electrode that thickness is 0.5mm.With tablet press machine by with tablet press machine by the pressure system 5 ~ 10min of air electrode at 2 ~ 5MPa.Air electrode through compacting is put into vacuum drying chamber, is warming up to 50 DEG C, vacuumize 30 ~ 50min, obtain dry air electrode.According to a conventional method air electrode and pure zine plate are assembled in battery case, inject the KOH electrolyte of 7M, obtain zinc and air cell.
Step 5, performance test.Carry out performance test to the air electrode obtained and zinc and air cell, content measurement comprises volt-ampere curve test and discharge curve test.
When performance test is carried out to air electrode and zinc and air cell:
Volt-ampere curve is tested: adopt three-electrode system, and using fixing for reserved yellow gold nano-catalytic oxidant layer sample on a rotary disc as work electrode negative electrode, platinum line is as anode, and with saturated calomel for reference electrode, electrolyte is the 0.1mol L that oxygen is saturated -1potassium hydroxide aqueous solution.Successively the rotating speed of rotating circular disk be 400,800,1600,2400 and 3200rpm condition under, use CHI660C type electrochemical workstation to do the test of Linear volt-ampere curve, obtain the linear volt-ampere curve of rotating circular disk of the oxygen reduction reaction catalytic activity of catalyst layer.
Discharge curve is tested: use BTS battery measurement system, measure zinc and air cell according to a conventional method, obtain the discharge curve of yellow gold nano-catalytic oxidant layer in monomer zinc and air cell.
The present invention adopts pulse laser sediment method, directly silver-copper nano alloy is deposited on nickel foam afflux and extremely goes up, prepared the cathode catalyst layer of silver-bearing copper single phase solid solution alloying, forms not carbon containing and the Catalytic Layer containing Teflon.
The microstructure of the silver-copper nano alloy film that the present invention deposits in nickel foam is that silver-copper nano alloy phase is of a size of 2.8 nanometers, and crystal structure is face-centred cubic structure ordered solid solution, and composition is Ag in glassy Cu matrix homodisperse silver-copper nano alloy phase 100-xcu x, the combination of x=10-50, Ag 3d electronics can be 379.97 and the combination of 374.27eV, Cu 2p electronics can be 965.17 and 952.47eV..The open circuit voltage of silver-copper nano alloy film in a zinc and air cell is 1.42 ~ 1.44V, and power density reaches as high as 86.3mW.cm -2, the charge and discharge cycles efficiency in secondary zinc and air cell is greater than 41%.
This invention exploits a kind of new cathode catalyst layer, and improve the preparation method of conventional catalyst oxidant layer, silver is used to replace gold, the noble metals such as platinum, use vapour deposition process (PLD) to replace solwution method and electrodeposition process to prepare silver-bearing copper cathode catalyst layer as air battery cathode Catalytic Layer.Compare solwution method and electrodeposition process technology, use gaseous techniques to prepare silver-bearing copper cathode catalyst layer, improve the accuracy controlling Catalytic Layer composition, structure and image, shorten manufacturing cycle, preparation process automation can be made.In Catalytic Layer, carbon containing does not effectively avoid the problem of the carbon of nascent state oxygen meeting strong corrosion air electrode simultaneously.The present invention uses linear sweep voltammetry and rotating disk electrode (r.d.e) to test prepared cathode catalysis layer.Acquisition composition is Ag 90cu 10and Ag 50cu 50the linear volt-ampere analysis of RDE of the oxygen reduction reaction catalytic performance of catalyst layer as shown in Figures 2 and 3, Ag 90cu 10and Ag 50cu 50the oxygen reduction reaction of catalyst layer is diffusion control, and static reduction current is 5.6 and 5.9mA cm -2, oxygen reduction reaction dynamics electric transmission number is 4 and 3.9.During Ag is catalyst based, electric transmission number is about 4 is the keys passing judgment on catalytic efficiency, and this result shows Ag 90cu 10and Ag 50cu 50catalyst layer has good catalytic effect.As shown in Figure 4, open circuit voltage is 1.42V and 1.44V to the discharge performance result of combined catalyst layer in zinc and air cell, and power density reaches as high as 86.3mW.cm -2and 82.1mW.cm -2, charge and discharge cycles efficiency is more than 41%.The current density being at 1V discharge voltage is 60mA cm -2with 50mA cm -2.This discharge voltage relative to other Ag base products similar is high 0.2V, when power density improves 20%, 1V, current density improves 20-30mA cm -2(50%-60%).
Accompanying drawing explanation
Accompanying drawing 1 is the preparation flow figure of silver-copper nano alloy air-electrode catalyst layer.
Accompanying drawing 2 is compositions is Ag 90cu 10the linear volt-ampere curve of rotating circular disk of the oxygen reduction reaction catalytic activity of catalyst layer, in figure, curve 1 is 400rpm, and curve 2 is 800rpm, and curve 3 is 1600rpm, and curve 3 is 2400rpm, and curve 5 is 3200rpm.
Accompanying drawing 3 is compositions is Ag 50cu 50the linear volt-ampere curve of rotating circular disk of the oxygen reduction reaction catalytic activity of catalyst layer, in figure, curve 1 is 400rpm, and curve 2 is 800rpm, and curve 3 is 1600rpm, and curve 3 is 2400rpm, and curve 5 is 3200rpm.
Accompanying drawing 4 is Ag 90cu 10and Ag 50cu 50the discharge curve of catalyst layer in monomer zinc and air cell, in figure, curve 1 is Ag 50cu 50do catalyst layer cell power density curve, line 2 is Ag 90cu 10do catalyst layer cell power density-current density plot, line 3 is Ag 50cu 50do catalyst layer cell voltage-current density plot, line 4 is Ag 90cu 10do catalyst layer cell voltage-current density plot.
Accompanying drawing 5 is Ag 50cu 50the cycle efficieny test result of catalyst layer in zinc and air cell.
Embodiment
Embodiment 1
The present embodiment is a kind of silver-copper nano alloy air-electrode catalyst layer.
Described silver-copper nano alloy air-electrode catalyst layer is the film be made up of 50 ~ 90%Ag and 10 ~ 50%Cu, and described percentage is atomic percent.In the present embodiment, the atomic percent that the atomic percent of Ag is 90%, Cu is 10%.Through transmission electron microscope observing, the microstructure of described silver-copper nano alloy air-electrode catalyst layer be silver-copper nano alloy particle dispersion in the noncrystal substrate of copper, average nanoparticle particle diameter position 2.8nm, distribution particle diameter is between 1 ~ 5nm.
The present embodiment also proposed a kind of method preparing described silver-copper nano alloy air-electrode catalyst layer, and detailed process is:
Step 1, process nickel foam substrate.Getting thickness is that the nickel foam of 1mm is flooded 3h oil removing successively in acetone, soaked 15min remove oxide in the dilute sulfuric acid of 5%, and with deionized water rinsing, dries for subsequent use.
Step 2, pulsed laser deposition yellow gold nanocatalyst.The nickel foam substrate cleaned up is fixed on the sample stage of impulse laser deposition system, be that the yellow gold target of 5 ~ 9:5 ~ 1 is fixed on rotary target platform by atomic ratio, wherein yellow gold target is the yellow gold of the smelting process die casting that market is bought, in the present embodiment, the atomic ratio of yellow gold target is 9:1.The distance regulating substrate and target is 5cm.Open vacuum system, vacuum degree in vacuum chamber is extracted into 2.0*10 -4pa, makes target and substrate with the rotating speed uniform rotation of 5r/min.Block sample stage with baffle plate, unbalanced pulse laser, laser ablation target 2 minutes is to remove target material surface oxide.Take off baffle plate, the pulse duration arranging LASER Light Source is 6ns, laser repetition rate is 10Hz, pulsed laser deposition 45 ~ 120min, in the present embodiment, the pulsed laser deposition time is 45min, under the condition of continuous vacuum, sample is dropped to room temperature, in vacuum chamber, be filled with nitrogen take out sample, obtain yellow gold nano-catalytic oxidant layer.
Step 3, preparation air diffusion layer.Acetylene black mixes in the ratio of 1:2 ~ 3 with PTFE by the preparation method of air diffusion layer in absolute ethyl alcohol, ultrasonic disperse 15min, and magnetic rotor stirs 30min, obtains the mixture of acetylene black and PTFE.The mixture that the thermostat water bath mixture of acetylene black and PTFE being placed in 80 ~ 90 DEG C is incubated to described acetylene black and PTFE forms paste body shape, with roll squeezer, the mixture of the paste body shape acetylene black obtained and PTFE is pressed into the membranaceous air diffusion layer that thickness is 0.5 ~ 0.8mm.In the present embodiment, the ratio of acetylene black and PTFE is 1:2; The temperature of thermostat water bath is 80 DEG C; The thickness of the air diffusion layer obtained is 0.5mm.
Step 4, assembling zinc and air cell.The yellow gold nanocatalyst obtained is placed on air diffusion layer surface, with roll squeezer, catalyst layer and air diffusion layer is pressed into the membranaceous air electrode that thickness is 0.5mm.With tablet press machine by with tablet press machine by the pressure system 5 ~ 10min of air electrode at 2 ~ 5MPa, the present embodiment is at 2MPa pressure 10min.Air electrode through compacting is put into vacuum drying chamber, is warming up to 50 DEG C, vacuumize 30 ~ 50min, the present embodiment adopts 30min, obtains dry air electrode.According to a conventional method air electrode and pure zine plate are assembled in battery case, inject the KOH electrolyte of 7M, obtain zinc and air cell.
Step 5, performance test.Carry out performance test to the air electrode obtained and zinc and air cell, content measurement comprises volt-ampere curve test and discharge curve test.
Volt-ampere curve is tested: adopt three-electrode system, and using fixing for reserved yellow gold nano-catalytic oxidant layer sample on a rotary disc as work electrode negative electrode, platinum line is as anode, and with saturated calomel for reference electrode, electrolyte is the 0.1mol L that oxygen is saturated -1potassium hydroxide aqueous solution.Successively the rotating speed of rotating circular disk be 400,800,1600,2400 and 3200rpm condition under, use CHI660C type electrochemical workstation to do the test of Linear volt-ampere curve, obtain the linear volt-ampere curve of rotating circular disk of the oxygen reduction reaction catalytic activity of catalyst layer.
Discharge curve is tested: use BTS battery measurement system, measure zinc and air cell according to a conventional method, obtain the discharge curve of yellow gold nano-catalytic oxidant layer in monomer zinc and air cell.
Embodiment 2
The present embodiment is a kind of silver-copper nano alloy air-electrode catalyst layer.
Described silver-copper nano alloy air-electrode catalyst layer is the film be made up of 50 ~ 90%Ag and 10 ~ 50%Cu, and described percentage is atomic percent.In the present embodiment, the atomic percent that the atomic percent of Ag is 75%, Cu is 25%.Through transmission electron microscope observing, the microstructure of described silver-copper nano alloy air-electrode catalyst layer be silver-copper nano alloy particle dispersion in the noncrystal substrate of copper, average nanoparticle particle diameter is 2.5nm, and distribution particle diameter is between 1 ~ 5nm.
The present embodiment also proposed a kind of method preparing described silver-copper nano alloy air-electrode catalyst layer, and detailed process is:
Step 1, process nickel foam substrate.Getting thickness is that the nickel foam of 1mm is flooded 3h oil removing successively in acetone, soaked 15min remove oxide in the dilute sulfuric acid of 5%, and with deionized water rinsing, dries for subsequent use.
Step 2, pulsed laser deposition yellow gold nanocatalyst.The nickel foam substrate cleaned up is fixed on the sample stage of impulse laser deposition system, be that the yellow gold target of 5 ~ 9:5 ~ 1 is fixed on rotary target platform by atomic ratio, wherein yellow gold target is the yellow gold of the smelting process die casting that market is bought, in the present embodiment, the atomic ratio of yellow gold target is 7.5:2.5.The distance regulating substrate and target is 5cm.Open vacuum system, vacuum degree in vacuum chamber is extracted into 2.0*10-4Pa, makes target and substrate with the rotating speed uniform rotation of 5r/min.Block sample stage with baffle plate, unbalanced pulse laser, laser ablation target 2 minutes is to remove target material surface oxide.Take off baffle plate, the pulse duration arranging LASER Light Source is 6ns, laser repetition rate is 10Hz, pulsed laser deposition 45 ~ 120min, in the present embodiment, the pulsed laser deposition time is 70min, under the condition of continuous vacuum, sample is dropped to room temperature, in vacuum chamber, be filled with nitrogen take out sample, obtain yellow gold nano-catalytic oxidant layer.
Step 3, preparation air diffusion layer.Acetylene black mixes in the ratio of 1:2 ~ 3 with PTFE by the preparation method of air diffusion layer in absolute ethyl alcohol, ultrasonic disperse 15min, and magnetic rotor stirs 30min, obtains the mixture of acetylene black and PTFE.The mixture that the thermostat water bath mixture of acetylene black and PTFE being placed in 80 ~ 90 DEG C is incubated to described acetylene black and PTFE forms paste body shape, with roll squeezer, the mixture of the paste body shape acetylene black obtained and PTFE is pressed into the membranaceous air diffusion layer that thickness is 0.5 ~ 0.8mm.In the present embodiment, the ratio of acetylene black and PTFE is 1:2.5; The temperature of thermostat water bath is 90 DEG C; The thickness of the air diffusion layer obtained is 0.8mm.
Step 4, assembling zinc and air cell.The yellow gold nanocatalyst obtained is placed on air diffusion layer surface, with roll squeezer, catalyst layer and air diffusion layer is pressed into the membranaceous air electrode that thickness is 0.5mm.With tablet press machine by with tablet press machine by the pressure system 5 ~ 10min of air electrode at 2 ~ 5MPa, the present embodiment is at 5MPa pressure 5min.Air electrode through compacting is put into vacuum drying chamber, and be warming up to 50 DEG C, vacuumize 30 ~ 50min, the present embodiment adopts 40min, obtains dry air electrode.According to a conventional method air electrode and pure zine plate are assembled in battery case, inject the KOH electrolyte of 7Mol, obtain zinc and air cell.
Step 5, performance test.Carry out performance test to the air electrode obtained and zinc and air cell, content measurement comprises volt-ampere curve test and discharge curve test.
Volt-ampere curve is tested: adopt three-electrode system, and using fixing for reserved yellow gold nano-catalytic oxidant layer sample on a rotary disc as work electrode negative electrode, platinum line is as anode, and with saturated calomel for reference electrode, electrolyte is the 0.1mol L that oxygen is saturated -1potassium hydroxide aqueous solution.Successively the rotating speed of rotating circular disk be 400,800,1600,2400 and 3200rpm condition under, use CHI660C type electrochemical workstation to do the test of Linear volt-ampere curve, obtain the linear volt-ampere curve of rotating circular disk of the oxygen reduction reaction catalytic activity of catalyst layer.
Discharge curve is tested: use BTS battery measurement system, measure zinc and air cell according to a conventional method, obtain the discharge curve of yellow gold nano-catalytic oxidant layer in monomer zinc and air cell.
Embodiment 3
The present embodiment is a kind of silver-copper nano alloy air-electrode catalyst layer.
Described silver-copper nano alloy air-electrode catalyst layer is the film be made up of 50 ~ 90%Ag and 10 ~ 50%Cu, and described percentage is atomic percent.In the present embodiment, the atomic percent that the atomic percent of Ag is 50%, Cu is 50%.Through transmission electron microscope observing, the microstructure of described silver-copper nano alloy air-electrode catalyst layer be silver-copper nano alloy particle dispersion in the noncrystal substrate of copper, average nanoparticle particle diameter is 2.6nm, and distribution particle diameter is between 1 ~ 5nm.
The present embodiment also proposed a kind of method preparing described silver-copper nano alloy air-electrode catalyst layer, and detailed process is:
Step 1, process nickel foam substrate.Getting thickness is that the nickel foam of 1mm is flooded 3h oil removing successively in acetone, soaked 15min remove oxide in the dilute sulfuric acid of 5%, and with deionized water rinsing, dries for subsequent use.
Step 2, pulsed laser deposition yellow gold nanocatalyst.The nickel foam substrate cleaned up is fixed on the sample stage of impulse laser deposition system, be that the yellow gold target of 5 ~ 9:5 ~ 1 is fixed on rotary target platform by atomic ratio, wherein yellow gold target is the yellow gold of the smelting process die casting that market is bought, in the present embodiment, the atomic ratio of yellow gold target is 5:5.The distance regulating substrate and target is 5cm.Open vacuum system, vacuum degree in vacuum chamber is extracted into 2.0*10 -4pa, makes target and substrate with the rotating speed uniform rotation of 5r/min.Block sample stage with baffle plate, unbalanced pulse laser, laser ablation target 2 minutes is to remove target material surface oxide.Take off baffle plate, the pulse duration arranging LASER Light Source is 6ns, laser repetition rate is 10Hz, pulsed laser deposition 45 ~ 120min, in the present embodiment, the pulsed laser deposition time is 120min, under the condition of continuous vacuum, sample is dropped to room temperature, in vacuum chamber, be filled with nitrogen take out sample, obtain yellow gold nano-catalytic oxidant layer.
Step 3, preparation air diffusion layer.Acetylene black mixes in the ratio of 1:2 ~ 3 with PTFE by the preparation method of air diffusion layer in absolute ethyl alcohol, ultrasonic disperse 15min, and magnetic rotor stirs 30min, obtains the mixture of acetylene black and PTFE.The mixture that the thermostat water bath mixture of acetylene black and PTFE being placed in 80 ~ 90 DEG C is incubated to described acetylene black and PTFE forms paste body shape, with roll squeezer, the mixture of the paste body shape acetylene black obtained and PTFE is pressed into the membranaceous air diffusion layer that thickness is 0.5 ~ 0.8mm.In the present embodiment, the ratio of acetylene black and PTFE is 1:3; The temperature of thermostat water bath is 85 DEG C; The thickness of the air diffusion layer obtained is 0.6mm.
Step 4, assembling zinc and air cell.The yellow gold nanocatalyst obtained is placed on air diffusion layer surface, with roll squeezer, catalyst layer and air diffusion layer is pressed into the membranaceous air electrode that thickness is 0.5mm.With tablet press machine by with tablet press machine by the pressure system 5 ~ 10min of air electrode at 2 ~ 5MPa, the present embodiment is at 3.5MPa pressure 7min.Air electrode through compacting is put into vacuum drying chamber, and be warming up to 50 DEG C, vacuumize 30 ~ 50min, the present embodiment adopts 50min, obtains dry air electrode.According to a conventional method air electrode and pure zine plate are assembled in battery case, inject the KOH electrolyte of 7M, obtain zinc and air cell.
Step 5, performance test.Carry out performance test to the air electrode obtained and zinc and air cell, content measurement comprises volt-ampere curve test and discharge curve test.
Volt-ampere curve is tested: adopt three-electrode system, and using fixing for reserved yellow gold nano-catalytic oxidant layer sample on a rotary disc as work electrode negative electrode, platinum line is as anode, and with saturated calomel for reference electrode, electrolyte is the 0.1mol L that oxygen is saturated -1potassium hydroxide aqueous solution.Successively the rotating speed of rotating circular disk be 400,800,1600,2400 and 3200rpm condition under, use CHI660C type electrochemical workstation to do the test of Linear volt-ampere curve, obtain the linear volt-ampere curve of rotating circular disk of the oxygen reduction reaction catalytic activity of catalyst layer.
Discharge curve is tested: use BTS battery measurement system, measure zinc and air cell according to a conventional method, obtain the discharge curve of yellow gold nano-catalytic oxidant layer in monomer zinc and air cell.

Claims (4)

1. a silver-copper nano alloy air-electrode catalyst layer, is characterized in that, described silver-copper nano alloy air-electrode catalyst layer is film-form, is made up of 50 ~ 90%Ag and 10 ~ 50%Cu, and described percentage is atomic percent.
2. silver-copper nano alloy air-electrode catalyst layer as claimed in claim 1, it is characterized in that, the microstructure of described silver-copper nano alloy air-electrode catalyst layer is that silver-copper nano alloy particle dispersion is in the noncrystal substrate of copper, average nanoparticle particle diameter position 2.5 ~ 2.8nm, distribution particle diameter is between 1 ~ 5nm.
3. prepare a method for silver-copper nano alloy air-electrode catalyst layer described in claim 1, it is characterized in that, detailed process is:
Step 1, process nickel foam substrate;
Step 2, pulsed laser deposition yellow gold nanocatalyst; Being fixed on the sample stage of impulse laser deposition system by the nickel foam substrate cleaned up, is that the yellow gold target of 5 ~ 9:5 ~ 1 is fixed on rotary target platform by atomic ratio, and wherein yellow gold target is the yellow gold of the smelting process die casting that market is bought; The distance regulating substrate and target is 5cm; Open vacuum system, vacuum degree in vacuum chamber is extracted into 2.0*10 -4pa, makes target and substrate with the rotating speed uniform rotation of 5r/min; Block sample stage with baffle plate, unbalanced pulse laser, laser ablation target 2min is to remove target material surface oxide; Take off baffle plate, the pulse duration arranging LASER Light Source is 6ns, and laser repetition rate is 10Hz, pulsed laser deposition 45 ~ 120min, under the condition of continuous vacuum, drops to room temperature by sample, in vacuum chamber, be filled with nitrogen take out sample, obtain yellow gold nano-catalytic oxidant layer;
Step 3, preparation air diffusion layer; Acetylene black mixes in the ratio of 1:2 ~ 3 with PTFE by the preparation method of air diffusion layer in absolute ethyl alcohol, ultrasonic disperse 15min, and magnetic rotor stirs 30min, obtains the mixture of acetylene black and PTFE; The mixture that the thermostat water bath mixture of acetylene black and PTFE being placed in 80 ~ 90 DEG C is incubated to described acetylene black and PTFE forms paste body shape, with roll squeezer, the mixture of the paste body shape acetylene black obtained and PTFE is pressed into the membranaceous air diffusion layer that thickness is 0.5 ~ 0.8mm;
Step 4, assembling zinc and air cell; The yellow gold nanocatalyst obtained is placed on air diffusion layer surface, with roll squeezer, catalyst layer and air diffusion layer is pressed into the membranaceous air electrode that thickness is 0.5mm; With tablet press machine by with tablet press machine by the pressure system 5 ~ 10min of air electrode at 2 ~ 5MPa; Air electrode through compacting is put into vacuum drying chamber, is warming up to 50 DEG C, vacuumize 30 ~ 50min, obtain dry air electrode; According to a conventional method air electrode and pure zine plate are assembled in battery case, inject the KOH electrolyte of 7M, obtain zinc and air cell;
Step 5, performance test; To the air electrode obtained 1carry out performance test with zinc and air cell, content measurement comprises volt-ampere curve test and discharge curve test.
4. the preparation method of silver-copper nano alloy air-electrode catalyst layer as claimed in claim 3, is characterized in that, when carrying out performance test to air electrode and zinc and air cell:
Volt-ampere curve is tested: adopt three-electrode system, and using fixing for reserved yellow gold nano-catalytic oxidant layer sample on a rotary disc as work electrode negative electrode, platinum line is as anode, and with saturated calomel for reference electrode, electrolyte is the 0.1mol L that oxygen is saturated -1potassium hydroxide aqueous solution; Successively the rotating speed of rotating circular disk be 400,800,1600,2400 and 3200rpm condition under, use CHI660C type electrochemical workstation to do the test of Linear volt-ampere curve, obtain the linear volt-ampere curve of rotating circular disk of the oxygen reduction reaction catalytic activity of catalyst layer;
Discharge curve is tested: use BTS battery measurement system, measure zinc and air cell according to a conventional method, obtain the discharge curve of yellow gold nano-catalytic oxidant layer in monomer zinc and air cell.
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