CN104319408B - Silver-copper nano alloy air-electrode catalyst layer and its deposition process - Google Patents

Silver-copper nano alloy air-electrode catalyst layer and its deposition process Download PDF

Info

Publication number
CN104319408B
CN104319408B CN201410542528.1A CN201410542528A CN104319408B CN 104319408 B CN104319408 B CN 104319408B CN 201410542528 A CN201410542528 A CN 201410542528A CN 104319408 B CN104319408 B CN 104319408B
Authority
CN
China
Prior art keywords
silver
air
catalyst layer
copper nano
nano alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410542528.1A
Other languages
Chinese (zh)
Other versions
CN104319408A (en
Inventor
陈福义
吴小强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwestern Polytechnical University
Original Assignee
Northwestern Polytechnical University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northwestern Polytechnical University filed Critical Northwestern Polytechnical University
Priority to CN201410542528.1A priority Critical patent/CN104319408B/en
Publication of CN104319408A publication Critical patent/CN104319408A/en
Application granted granted Critical
Publication of CN104319408B publication Critical patent/CN104319408B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)
  • Catalysts (AREA)

Abstract

A kind of silver-copper nano alloy air-electrode catalyst layer and its deposition process.The 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.Silver-copper nano alloy directly is deposited on into nickel foam afflux using pulse laser sediment method extremely to go up, the cathode catalyst layer of silver-bearing copper single phase solid solution alloying is prepared for, not carbon containing and containing Teflon Catalytic Layer is formed.The microstructure of silver-copper nano alloy air-electrode catalyst layer is dispersed in the noncrystal substrate of copper for silver-copper nano alloy particle, 2.5~2.8nm of average nanoparticle particle diameter position, and distribution particle diameter is between 1~5nm.Open-circuit voltage of the 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, 20% is improved, the charge and discharge cycles efficiency in secondary zinc and air cell is more than 41%.

Description

Silver-copper nano alloy air-electrode catalyst layer and its deposition process
Technical field
The invention belongs to rechargeable metal and regeneratable fuel cell field, oxygen electricity in specifically above-mentioned battery Catalyst layer used on pole and air electrode and preparation method thereof.
Background technology
In recent years, due to energy environment crisis, pollution of traditional old and useless battery to environment is big, and regenerative resource such as light There are intermittent problems and cause that Development of Novel renewable energy device turns into the focus of energy field research in volt, wind energy etc.. Under natural conditions, metal-air battery and fuel cell oxidized metal or fuel can produce electronics on anode, while in the moon Oxygen is reduced on electrode catalyst layer, hydroxide ion or water is produced, and chemical energy is converted into electric energy.Due to anode metal or Oxidized is that the catalytic efficiency of the oxygen reduction reaction of catalyst layer in a spontaneous process, therefore air cell is influence battery The key of performance.Whole reaction in above process is spontaneous without extra energy, while cathode reaction consumption is oxygen Gas, generation be water or hydroxyl to the pollution-free of environment, it is sustainable, with the energy for fully solving current energy environment issues Power.Current cathod catalyst is mainly with Pt/C as catalyst, but metal platinum is expensive and scarcity of resources, constrains Pt The commercial applications argent prices of base catalyst only have 1st/50th of Pt, have in alkaline solution not worse than platinum Oxygen reduction reaction electrocatalytic properties, silver and silver-base alloy have begun 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, in ACS Appl.Mater.Interfaces delivers " Synthesis of Octopus-Tentacle-Like Cu Nanowire-Ag Nanocrystals Heterostructures and their Enhanced Electrocatalytic Performance For Oxygen Reduction Reaction ", this article is synthesized bimetallic Ag-Cu nanostructureds by solution reduction, During XRD analysis show nanostructured Ag and Cu is split-phase segregation, it was demonstrated that the ORR catalysis activities of Ag-Cu nano-catalytics layer are high In Ag/C.At present, for the research of silver-based nano-alloy cathode catalyst layer and preparation method thereof have been achieved for it is certain into Really.Northwestern Polytechnical University discloses a kind of fuel cell silver-bearing copper in the patent of invention of Patent No. ZL201110051634.6 Nano-alloy cathode and preparation method thereof, the method has been synthesized with silver-colored face-centred cubic structure silver-bearing copper by electrochemical deposition method Nanodendrites, in alkaline electrolyte, experimental studies have found that silver-bearing copper bimetal nano alloy is to H2O2There is oxygen reduction reaction catalysis Property, the air electrode catalyst United States Patent (USP)s US8685575B2 that can serve as fuel cell discloses a kind of fuel cell sky The catalyst layer component of pneumoelectric pole, active component is Ag and CoTMPP, carbon containing 50-80%, 2-20% containing Teflon, in circulation alkali Under the operating condition of property electrolyte and zinc raw material, monocell can be in 280mA/cm2Under conditions of, reach 1 volt of voltage.In application Number the zinc sky metal fuel battery oxygen electrodes that a kind of heat seal process method makes are reported for 200620004676.9.Afflux extremely steeps Foam nickel, by silver, copper, the nitrate of manganese etc. is decomposed and formed catalyst layer, and carbon containing is 50-94%, 10-30% containing Teflon, rolling Into 0.1-0.2 millimeters of film.Northwestern Polytechnical University is in patent No. CN102321825A by controlling alloy composition to modulate this Alloy surface plasmon resonant frequency, with the increase of silver content ratio in yellow gold, alloy plasma absworption peak occurs red Move.The silver-copper nano dendrite for being formed has the coarse, surface of cleaning and big specific surface area, on Surface-enhanced spectroscopic, surface Plasma-Optical is catalyzed and surface plasma strengthens the aspects such as solar absorption and has preferably application.Northwestern Polytechnical University is special Profit CN102157740A prepares copper silver nanoparticle alloy catalyst using electrochemical deposition method, and as sodium borohydride/ The cathod catalyst of hydrogen peroxide as fuel battery, is effectively reduced answering for sodium borohydride/hydrogen peroxide as fuel cell cathode elctro-catalyst With cost, and excellent catalytic effect.
Although silver and silver-base alloy have had preliminary experiment as air electrode catalyst, its catalysis activity and resistance to Long property can not meet wide variety of commercial requirements.Existing air electrode cathod catalyst technology of preparing catalyst component, Preparation technology with there is following key issue with the carrier use of the catalyst layer:
(1) on air electrode catalyst composition, there be not and copper, manganese the silver element of silver-base alloy catalyst in current document These can make to be conducive to Ag alloyings, form the transition metal of stably catalyzed oxidant layer.Meanwhile, the d orbit centres of fine silver are satisfied Relatively low with spending, the absorption to oxygen is weak, and oxygen reduction reaction catalysis activity is weaker, and it is new come development of adulterating that silver needs suitable metallic element Silver-base alloy nanocatalyst improve its catalysis activity
(2) in air-electrode catalyst layer preparation technology, the synthesis of silver alloy elctro-catalyst is related to craft in current document Operation and solution process, without causing to prepare the characteristic that cell process is automated, while technique is difficult to control, are unfavorable for parameter Setup module, energy density and circulation longevity that elctro-catalyst and its prototype battery prepared by laboratory stage application is likely to be breached Life, it is impossible to it is contemplated that realizing in yield production type battery
(3) on air-electrode catalyst layer carrier, current silver-base alloy largely uses various forms of carbon (such as acetylene black And electrically conductive graphite) catalyst carrier is done, when air cell charges, oxygen can be produced in the afflux extremely nickel foam of air electrode Gas, the carbon of nascent state oxygen meeting strong corrosion air electrode, causes Ag base catalytic active components to come off, through making after a while With the catalysis activity of air electrode can be significantly reduced.
The content of the invention
To overcome the shortcomings of the unstable properties of air electrode present in prior art, being unsuitable for automated production, this Invention proposes a kind of silver-copper nano alloy air-electrode catalyst layer and its deposition process.
The silver-copper nano alloy air-electrode catalyst layer is film-form, by 50~90%Ag and 10~50%Cu groups Into described percentage is atomic percent.
The microstructure of the silver-copper nano alloy air-electrode catalyst layer is dispersed in copper for silver-copper nano alloy particle Noncrystal substrate in, average nanoparticle particle diameter position 2.5~2.8nm, distribution particle diameter between 1~5nm.
Preparing the silver-copper nano alloy air-electrode catalyst layer detailed process is：
Step 1, processes nickel foam substrate.
Step 2, pulsed laser deposition yellow gold nanocatalyst.The nickel foam substrate that will be cleaned up is fixed on pulse It is 5~9 by atomic ratio on the sample stage of laser deposition system：5~1 yellow gold target is fixed on rotary target platform, wherein silver Copper alloy target is the yellow gold of the smelting process die casting of market purchase.Regulation substrate is 5cm with the distance of target.Open vacuum System, 2.0*10 is extracted into by vacuum in vacuum chamber-4Pa, makes target and substrate with the rotating speed uniform rotation of 5r/min.Use baffle plate Block sample stage, unbalanced pulse laser, laser ablation target 2min is removing target material surface oxide.Baffle plate is removed, is set The pulse width of LASER Light Source is 6ns, and laser repetition rate is 10Hz, 45~120min of pulsed laser deposition, in continuous vacuum Under conditions of, sample is dropped into room temperature, sample is taken out to nitrogen is filled with vacuum chamber, obtain yellow gold nano-catalytic oxidant layer.
Step 3, prepares air diffusion layer.The preparation method of air diffusion layer is by 1 by acetylene black and PTFE:2~3 ratio Example mixes in absolute ethyl alcohol, ultrasonic disperse 15min, magnetic rotor stirring 30min, obtains the mixture of acetylene black and PTFE. The mixture of acetylene black and PTFE is placed in 80~90 DEG C of thermostat water bath the mixing being incubated to the acetylene black and PTFE Thing forms paste body shape, and the paste body shape acetylene black that will be obtained with roll squeezer is pressed into thickness for 0.5~0.8mm with the mixture of PTFE Membranaceous air diffusion layer.
Step 4, assembles zinc and air cell.The yellow gold nanocatalyst that will be obtained is placed on air diffusion layer surface, uses Catalyst layer and air diffusion layer are pressed into roll squeezer the membranaceous air electrode that thickness is 0.5mm.Compressing tablet will be used with tablet press machine Air electrode is suppressed 5~10min by machine under the pressure of 2~5MPa.Vacuum drying chamber will be put into by the air electrode of compacting In, 50 DEG C are warming up to, 30~50min is vacuum dried, obtain dry air electrode.According to a conventional method by air electrode and pure zinc Plate is assembled into battery case, injects the KOH electrolyte of 7M, obtains zinc and air cell.
Step 5, performance test.Air electrode and zinc and air cell to obtaining carry out performance test, and test content includes volt The test of peace curve and discharge curve test.
When carrying out performance test to air electrode and zinc and air cell：
Volt-ampere curve is tested：Using three-electrode system, reserved yellow gold nano-catalytic oxidant layer sample is fixed on rotation Turn as working electrode negative electrode on disk, used as anode, with saturation calomel as reference electrode, electrolyte is oxygen saturation to platinum line 0.1mol L-1Potassium hydroxide aqueous solution.The rotating speed in rotating circular disk is 400,800,1600,2400 and 3200rpm successively Under the conditions of, make upper linear volt-ampere curve using CHI660C types electrochemical workstation and test, obtain the oxygen reduction reaction of catalyst layer The linear volt-ampere curve of rotating circular disk of catalysis activity.
Discharge curve is tested：Using BTS battery measurement systems, zinc and air cell is measured according to a conventional method, obtain yellow gold Discharge curve of the nano-catalytic oxidant layer in monomer zinc and air cell.
The present invention uses pulse laser sediment method, and silver-copper nano alloy directly is deposited on into nickel foam afflux extremely goes up, system For the cathode catalyst layer of silver-bearing copper single phase solid solution alloying, not carbon containing and containing Teflon Catalytic Layer is formed.
The microstructure of the silver-copper nano alloy film that the present invention is deposited in nickel foam is uniformly to divide in amorphous Copper substrate Scattered silver-copper nano alloy phase, the size of silver-copper nano alloy phase is 2.8 nanometers, and crystal structure is face-centred cubic structure solid in order Solution, composition is Ag100-xCux, the combination of x=10-50, Ag 3d electronics can be 379.97 and 374.27eV, Cu 2p electronics With reference to can be 965.17 and 952.47eV..Open-circuit voltage of the silver-copper nano alloy film in a zinc and air cell be 1.42~ 1.44V, power density reaches as high as 86.3mW.cm-2, the charge and discharge cycles efficiency in secondary zinc and air cell is more than 41%.
The present invention develops a kind of new cathode catalyst layer, and improves the preparation method of conventional catalyst oxidant layer, uses Silver replaces the noble metals such as gold, platinum, and silver-bearing copper cathod catalyst is prepared instead of solwution method and electrodeposition process using vapour deposition process (PLD) Layer is used as air battery cathode Catalytic Layer.Compared to solwution method and electrodeposition process technology, prepare silver-bearing copper negative electrode using gaseous techniques and urge Agent layer, improves the accuracy of control catalysis composition of layer, structure and image, shortens manufacturing cycle, can make preparation process Automation.It is simultaneously not carbon containing in Catalytic Layer effectively to avoid the problem that nascent state oxygen understands the carbon of strong corrosion air electrode. The present invention is tested using linear sweep voltammetry and rotating disk electrode (r.d.e) to prepared cathode catalysis layer.Obtain composition It is Ag90Cu10And Ag50Cu50The linear volt-ampere analysis of RDE of the oxygen reduction reaction catalytic performance of catalyst layer as shown in Figures 2 and 3, Ag90Cu10And Ag50Cu50The 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.In Ag base catalyst, electric transmission number is to judge catalysis for 4 or so The key of efficiency, the result shows Ag90Cu10And Ag50Cu50Catalyst layer has good catalytic effect.Combined catalyst layer exists As shown in figure 4, open-circuit voltage is 1.42V and 1.44V, power density is reached as high as discharge performance result in zinc and air cell 86.3mW.cm-2And 82.1mW.cm-2, charge and discharge cycles efficiency is more than 41%.The current density for being in 1V discharge voltages is 60mA cm-2With 50mA cm-2.This is high relative to the discharge voltage of similar other Ag base products 0.2V, power density is improved Current density improves 20-30mA cm when 20%, 1V-2(50%-60%).
Brief description of the drawings
Accompanying drawing 1 is the preparation flow figure of silver-copper nano alloy air-electrode catalyst layer.
Accompanying drawing 2 is that composition is Ag90Cu10The linear volt-ampere of rotating circular disk of the oxygen reduction reaction catalysis activity of catalyst layer is bent Line, curve 1 is 400rpm in figure, and curve 2 is 800rpm, and curve 3 is 1600rpm, and curve 3 is 2400rpm, and curve 5 is 3200rpm。
Accompanying drawing 3 is that composition is Ag50Cu50The linear volt-ampere of rotating circular disk of the oxygen reduction reaction catalysis activity of catalyst layer is bent Line, curve 1 is 400rpm in figure, and curve 2 is 800rpm, and curve 3 is 1600rpm, and curve 3 is 2400rpm, and curve 5 is 3200rpm。
Accompanying drawing 4 is Ag90Cu10And Ag50Cu50Discharge curve of the catalyst layer in monomer zinc and air cell, curve 1 is in figure Ag50Cu50Catalyst layer cell power density curve is done, line 2 is Ag90Cu10Do catalyst layer cell power density-current density Curve, line 3 is Ag50Cu50Catalyst layer cell voltage-current density plot is done, line 4 is Ag90Cu10Do catalyst layer battery electricity Piezo-electric current density curve.
Accompanying drawing 5 is Ag50Cu50Cycle efficieny test result of the catalyst layer in zinc and air cell.
Specific embodiment
Embodiment 1
The present embodiment is a kind of silver-copper nano alloy air-electrode catalyst layer.
The silver-copper nano alloy air-electrode catalyst layer is the film being made up of 50~90%Ag and 10~50%Cu, Described percentage is atomic percent.In the present embodiment, the atomic percent that the atomic percent of Ag is 90%, Cu is 10%.By transmission electron microscope observing, the microstructure of the silver-copper nano alloy air-electrode catalyst layer is silver-copper nano conjunction Gold particle is dispersed in the noncrystal substrate of copper, average nanoparticle particle diameter position 2.8nm, and distribution particle diameter is between 1~5nm.
The present embodiment also proposed a kind of method for preparing the silver-copper nano alloy air-electrode catalyst layer, specific mistake Cheng Shi：
Step 1, processes nickel foam substrate.Take nickel foam that thickness is 1mm successively in acetone dipping 3h oil removings, 5% Dilute sulfuric acid in soak 15min removal oxides, and use deionized water rinsing, dry standby.
Step 2, pulsed laser deposition yellow gold nanocatalyst.The nickel foam substrate that will be cleaned up is fixed on pulse It is 5~9 by atomic ratio on the sample stage of laser deposition system：5~1 yellow gold target is fixed on rotary target platform, wherein silver Copper alloy target is the yellow gold of the smelting process die casting of market purchase, and in the present embodiment, the atomic ratio of yellow gold target is 9:1.Regulation substrate is 5cm with the distance of target.Vacuum system is opened, vacuum in vacuum chamber is extracted into 2.0*10-4Pa, makes target With substrate with the rotating speed uniform rotation of 5r/min.Sample stage, unbalanced pulse laser, 2 points of laser ablation target are blocked with baffle plate Clock is removing target material surface oxide.Baffle plate is removed, the pulse width for setting LASER Light Source is 6ns, and laser repetition rate is 10Hz, 45~120min of pulsed laser deposition, the pulsed laser deposition time is 45min in the present embodiment, in the bar of continuous vacuum Under part, sample is dropped into room temperature, sample is taken out to nitrogen is filled with vacuum chamber, obtain yellow gold nano-catalytic oxidant layer.
Step 3, prepares air diffusion layer.The preparation method of air diffusion layer is by 1 by acetylene black and PTFE:2~3 ratio Example mixes in absolute ethyl alcohol, ultrasonic disperse 15min, magnetic rotor stirring 30min, obtains the mixture of acetylene black and PTFE. The mixture of acetylene black and PTFE is placed in 80~90 DEG C of thermostat water bath the mixing being incubated to the acetylene black and PTFE Thing forms paste body shape, and the paste body shape acetylene black that will be obtained with roll squeezer is pressed into thickness for 0.5~0.8mm with the mixture of PTFE Membranaceous air diffusion layer.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 for arriving is 0.5mm.
Step 4, assembles zinc and air cell.The yellow gold nanocatalyst that will be obtained is placed on air diffusion layer surface, uses Catalyst layer and air diffusion layer are pressed into roll squeezer the membranaceous air electrode that thickness is 0.5mm.Compressing tablet will be used with tablet press machine Air electrode is suppressed 5~10min by machine under the pressure of 2~5MPa, and the present embodiment suppresses 10min under 2MPa pressure.Will be through The air electrode for crossing compacting is put into vacuum drying chamber, is warming up to 50 DEG C, is vacuum dried 30~50min, and the present embodiment is used 30min, obtains dry air electrode.Air electrode and pure zine plate are assembled into battery case according to a conventional method, injection 7M's KOH electrolyte, obtains zinc and air cell.
Step 5, performance test.Air electrode and zinc and air cell to obtaining carry out performance test, and test content includes volt The test of peace curve and discharge curve test.
Volt-ampere curve is tested：Using three-electrode system, reserved yellow gold nano-catalytic oxidant layer sample is fixed on rotation Turn as working electrode negative electrode on disk, used as anode, with saturation calomel as reference electrode, electrolyte is oxygen saturation to platinum line 0.1mol L-1Potassium hydroxide aqueous solution.The rotating speed in rotating circular disk is 400,800,1600,2400 and 3200rpm successively Under the conditions of, make upper linear volt-ampere curve using CHI660C types electrochemical workstation and test, obtain the oxygen reduction reaction of catalyst layer The linear volt-ampere curve of rotating circular disk of catalysis activity.
Discharge curve is tested：Using BTS battery measurement systems, zinc and air cell is measured according to a conventional method, obtain yellow gold Discharge curve of the 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.
The silver-copper nano alloy air-electrode catalyst layer is the film being made up of 50~90%Ag and 10~50%Cu, Described percentage is atomic percent.In the present embodiment, the atomic percent that the atomic percent of Ag is 75%, Cu is 25%.By transmission electron microscope observing, the microstructure of the silver-copper nano alloy air-electrode catalyst layer is silver-copper nano conjunction Gold particle is dispersed in the noncrystal substrate of copper, and average nanoparticle particle diameter is 2.5nm, and distribution particle diameter is between 1~5nm.
The present embodiment also proposed a kind of method for preparing the silver-copper nano alloy air-electrode catalyst layer, specific mistake Cheng Shi：
Step 1, processes nickel foam substrate.Take nickel foam that thickness is 1mm successively in acetone dipping 3h oil removings, 5% Dilute sulfuric acid in soak 15min removal oxides, and use deionized water rinsing, dry standby.
Step 2, pulsed laser deposition yellow gold nanocatalyst.The nickel foam substrate that will be cleaned up is fixed on pulse It is 5~9 by atomic ratio on the sample stage of laser deposition system：5~1 yellow gold target is fixed on rotary target platform, wherein silver Copper alloy target is the yellow gold of the smelting process die casting of market purchase, and in the present embodiment, the atomic ratio of yellow gold target is 7.5:2.5.Regulation substrate is 5cm with the distance of target.Vacuum system is opened, vacuum in vacuum chamber is extracted into 2.0*10-4Pa, Make target and substrate with the rotating speed uniform rotation of 5r/min.Sample stage, unbalanced pulse laser, target for laser ablation are blocked with baffle plate Material 2 minutes is removing target material surface oxide.Baffle plate is removed, the pulse width for setting LASER Light Source is 6ns, laser repetition rate It is 10Hz, 45~120min of pulsed laser deposition, the pulsed laser deposition time is 70min in the present embodiment, in continuous vacuum Under the conditions of, sample is dropped into room temperature, sample is taken out to nitrogen is filled with vacuum chamber, obtain yellow gold nano-catalytic oxidant layer.
Step 3, prepares air diffusion layer.The preparation method of air diffusion layer is by 1 by acetylene black and PTFE:2~3 ratio Example mixes in absolute ethyl alcohol, ultrasonic disperse 15min, magnetic rotor stirring 30min, obtains the mixture of acetylene black and PTFE. The mixture of acetylene black and PTFE is placed in 80~90 DEG C of thermostat water bath the mixing being incubated to the acetylene black and PTFE Thing forms paste body shape, and the paste body shape acetylene black that will be obtained with roll squeezer is pressed into thickness for 0.5~0.8mm with the mixture of PTFE Membranaceous air diffusion layer.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 for obtaining is 0.8mm.
Step 4, assembles zinc and air cell.The yellow gold nanocatalyst that will be obtained is placed on air diffusion layer surface, uses Catalyst layer and air diffusion layer are pressed into roll squeezer the membranaceous air electrode that thickness is 0.5mm.Compressing tablet will be used with tablet press machine Air electrode is suppressed 5~10min by machine under the pressure of 2~5MPa, and the present embodiment suppresses 5min under 5MPa pressure.To pass through The air electrode of compacting is put into vacuum drying chamber, is warming up to 50 DEG C, is vacuum dried 30~50min, and the present embodiment adopts 40min, Obtain dry air electrode.Air electrode and pure zine plate are assembled into battery case according to a conventional method, inject the KOH electricity of 7Mol Solution liquid, obtains zinc and air cell.
Step 5, performance test.Air electrode and zinc and air cell to obtaining carry out performance test, and test content includes volt The test of peace curve and discharge curve test.
Volt-ampere curve is tested：Using three-electrode system, reserved yellow gold nano-catalytic oxidant layer sample is fixed on rotation Turn as working electrode negative electrode on disk, used as anode, with saturation calomel as reference electrode, electrolyte is oxygen saturation to platinum line 0.1mol L-1Potassium hydroxide aqueous solution.The rotating speed in rotating circular disk is 400,800,1600,2400 and 3200rpm successively Under the conditions of, make upper linear volt-ampere curve using CHI660C types electrochemical workstation and test, obtain the oxygen reduction reaction of catalyst layer The linear volt-ampere curve of rotating circular disk of catalysis activity.
Discharge curve is tested：Using BTS battery measurement systems, zinc and air cell is measured according to a conventional method, obtain yellow gold Discharge curve of the 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.
The silver-copper nano alloy air-electrode catalyst layer is the film being made up of 50~90%Ag and 10~50%Cu, Described percentage is atomic percent.In the present embodiment, the atomic percent that the atomic percent of Ag is 50%, Cu is 50%.By transmission electron microscope observing, the microstructure of the silver-copper nano alloy air-electrode catalyst layer is silver-copper nano conjunction Gold particle is dispersed in the noncrystal substrate of copper, and average nanoparticle particle diameter is 2.6nm, and distribution particle diameter is between 1~5nm.
The present embodiment also proposed a kind of method for preparing the silver-copper nano alloy air-electrode catalyst layer, specific mistake Cheng Shi：
Step 1, processes nickel foam substrate.Take nickel foam that thickness is 1mm successively in acetone dipping 3h oil removings, 5% Dilute sulfuric acid in soak 15min removal oxides, and use deionized water rinsing, dry standby.
Step 2, pulsed laser deposition yellow gold nanocatalyst.The nickel foam substrate that will be cleaned up is fixed on pulse It is 5~9 by atomic ratio on the sample stage of laser deposition system：5~1 yellow gold target is fixed on rotary target platform, wherein silver Copper alloy target is the yellow gold of the smelting process die casting of market purchase, and in the present embodiment, the atomic ratio of yellow gold target is 5:5.Regulation substrate is 5cm with the distance of target.Vacuum system is opened, vacuum in vacuum chamber is extracted into 2.0*10-4Pa, makes target With substrate with the rotating speed uniform rotation of 5r/min.Sample stage, unbalanced pulse laser, 2 points of laser ablation target are blocked with baffle plate Clock is removing target material surface oxide.Baffle plate is removed, the pulse width for setting LASER Light Source is 6ns, and laser repetition rate is 10Hz, 45~120min of pulsed laser deposition, the pulsed laser deposition time is 120min in the present embodiment, in the bar of continuous vacuum Under part, sample is dropped into room temperature, sample is taken out to nitrogen is filled with vacuum chamber, obtain yellow gold nano-catalytic oxidant layer.
Step 3, prepares air diffusion layer.The preparation method of air diffusion layer is by 1 by acetylene black and PTFE:2~3 ratio Example mixes in absolute ethyl alcohol, ultrasonic disperse 15min, magnetic rotor stirring 30min, obtains the mixture of acetylene black and PTFE. The mixture of acetylene black and PTFE is placed in 80~90 DEG C of thermostat water bath the mixing being incubated to the acetylene black and PTFE Thing forms paste body shape, and the paste body shape acetylene black that will be obtained with roll squeezer is pressed into thickness for 0.5~0.8mm with the mixture of PTFE Membranaceous air diffusion layer.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 for arriving is 0.6mm.
Step 4, assembles zinc and air cell.The yellow gold nanocatalyst that will be obtained is placed on air diffusion layer surface, uses Catalyst layer and air diffusion layer are pressed into roll squeezer the membranaceous air electrode that thickness is 0.5mm.Compressing tablet will be used with tablet press machine Air electrode is suppressed 5~10min by machine under the pressure of 2~5MPa, and the present embodiment suppresses 7min under 3.5MPa pressure.Will be through The air electrode for crossing compacting is put into vacuum drying chamber, is warming up to 50 DEG C, is vacuum dried 30~50min, and the present embodiment is adopted 50min, obtains dry air electrode.Air electrode and pure zine plate are assembled into battery case according to a conventional method, injection 7M's KOH electrolyte, obtains zinc and air cell.
Step 5, performance test.Air electrode and zinc and air cell to obtaining carry out performance test, and test content includes volt The test of peace curve and discharge curve test.
Volt-ampere curve is tested：Using three-electrode system, reserved yellow gold nano-catalytic oxidant layer sample is fixed on rotation Turn as working electrode negative electrode on disk, used as anode, with saturation calomel as reference electrode, electrolyte is oxygen saturation to platinum line 0.1mol L-1Potassium hydroxide aqueous solution.The rotating speed in rotating circular disk is 400,800,1600,2400 and 3200rpm successively Under the conditions of, make upper linear volt-ampere curve using CHI660C types electrochemical workstation and test, obtain the oxygen reduction reaction of catalyst layer The linear volt-ampere curve of rotating circular disk of catalysis activity.
Discharge curve is tested：Using BTS battery measurement systems, zinc and air cell is measured according to a conventional method, obtain yellow gold Discharge curve of the nano-catalytic oxidant layer in monomer zinc and air cell.

Claims (1)

1. a kind of silver-copper nano alloy air-electrode catalyst layer, the silver-copper nano alloy air-electrode catalyst layer is film Shape, including silver-copper nano alloy, it is characterised in that the silver-copper nano alloy air-electrode catalyst layer is to close silver-copper nano Gold be deposited on nickel foam afflux extremely on obtain；The ratio of Ag is 90% or 75% or 50%, Cu in the silver-copper nano alloy Ratio is 10% or 25% or 50%；Described percentage is atomic percent；
The microstructure of the silver-copper nano alloy air-electrode catalyst layer is dispersed in the non-of copper for silver-copper nano alloy particle In brilliant matrix, average nanoparticle particle diameter is 2.5~2.8nm, and distribution particle diameter is between 1~5nm；
Preparation process using the zinc and air cell of the silver-copper nano alloy air-electrode catalyst layer is：
Step 1, processes nickel foam substrate；
Step 2, pulsed laser deposition yellow gold nanocatalyst；The nickel foam substrate that will be cleaned up is fixed on pulse laser It is 5~9 by atomic ratio on the sample stage of depositing system：5~1 yellow gold target is fixed on rotary target platform, and wherein silver-bearing copper is closed Gold target is the yellow gold of smelting process die casting；Regulation substrate is 5cm with the distance of target；Vacuum system is opened, by vacuum chamber Interior vacuum is extracted into 2.0*10-4Pa, makes target and substrate with the rotating speed uniform rotation of 5r/min；Sample stage is blocked with baffle plate, is opened Open pulse laser, laser ablation target 2min is removing target material surface oxide；Baffle plate is removed, the pulse of LASER Light Source is set Width is 6ns, and laser repetition rate is 10Hz, 45~120min of pulsed laser deposition, under conditions of continuous vacuum, by sample Room temperature is dropped to, sample is taken out to nitrogen is filled with vacuum chamber, obtain yellow gold nano-catalytic oxidant layer；
Step 3, prepares air diffusion layer；The preparation method of air diffusion layer is by 1 by acetylene black and PTFE:2~3 ratio exists Mix in absolute ethyl alcohol, ultrasonic disperse 15min, magnetic rotor stirring 30min obtains the mixture of acetylene black and PTFE；By second Acetylene black is placed in 80~90 DEG C of thermostat water bath the mixture shape being incubated to the acetylene black and PTFE with the mixture of PTFE Into paste body shape, the paste body shape acetylene black that will be obtained with roll squeezer is pressed into the film that thickness is 0.5~0.8mm with the mixture of PTFE Shape air diffusion layer；
Step 4, assembles zinc and air cell；The yellow gold nanocatalyst that will be obtained is placed on air diffusion layer surface, uses roll-in Catalyst layer and air diffusion layer are pressed into machine the membranaceous air electrode that thickness is 0.5mm；With tablet press machine by air electrode 2 5~10min is suppressed under the pressure of~5MPa；To be put into vacuum drying chamber by the air electrode of compacting, be warming up to 50 DEG C, very Sky dries 30~50min, obtains dry air electrode；Air electrode and pure zine plate are assembled into battery case, injection 7M's KOH electrolyte, obtains zinc and air cell；
Step 5, performance test；Air electrode and zinc and air cell to obtaining carry out performance test, and test content includes that volt-ampere is bent Line is tested and discharge curve test.
CN201410542528.1A 2014-10-14 2014-10-14 Silver-copper nano alloy air-electrode catalyst layer and its deposition process Active CN104319408B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410542528.1A CN104319408B (en) 2014-10-14 2014-10-14 Silver-copper nano alloy air-electrode catalyst layer and its deposition process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410542528.1A CN104319408B (en) 2014-10-14 2014-10-14 Silver-copper nano alloy air-electrode catalyst layer and its deposition process

Publications (2)

Publication Number Publication Date
CN104319408A CN104319408A (en) 2015-01-28
CN104319408B true CN104319408B (en) 2017-07-07

Family

ID=52374612

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410542528.1A Active CN104319408B (en) 2014-10-14 2014-10-14 Silver-copper nano alloy air-electrode catalyst layer and its deposition process

Country Status (1)

Country Link
CN (1) CN104319408B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109817999B (en) * 2019-01-23 2022-04-08 西北工业大学 Silver-catalyzed magnalium layered hydroxide membrane formate fuel cell and preparation method thereof
CN115360364A (en) * 2022-10-21 2022-11-18 深圳市氢蓝时代动力科技有限公司 Preparation method of dendritic silver-manganese catalyst

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1983687A (en) * 2005-12-14 2007-06-20 中国科学院大连化学物理研究所 Production of aluminum/hydrogen peroxide fuel battery cathode
CN104084216A (en) * 2014-07-16 2014-10-08 西北工业大学 Silver copper nano alloy electro-catalyst and laser gas phase deposition method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070224495A1 (en) * 2006-03-22 2007-09-27 Gibbons Daniel W Zinc/air cell
CN102157740B (en) * 2011-03-03 2013-12-25 西北工业大学 Copper and silver nano-alloy cathode for fuel cell and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1983687A (en) * 2005-12-14 2007-06-20 中国科学院大连化学物理研究所 Production of aluminum/hydrogen peroxide fuel battery cathode
CN104084216A (en) * 2014-07-16 2014-10-08 西北工业大学 Silver copper nano alloy electro-catalyst and laser gas phase deposition method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"锌-空气电池空气电极的制备及研究";崔存仓;《中国优秀硕士学位论文全文数据库-工程科技Ⅰ辑》;20140315(第3期);第17-21页 *

Also Published As

Publication number Publication date
CN104319408A (en) 2015-01-28

Similar Documents

Publication Publication Date Title
Muthurasu et al. Fabrication of nonmetal-modulated dual metal–organic platform for overall water splitting and rechargeable zinc–air batteries
CN110227480B (en) Preparation method of NiMo hydrogen evolution electrocatalyst
Ye et al. A novel PtRuIr nanoclusters synthesized by selectively electrodepositing Ir on PtRu as highly active bifunctional electrocatalysts for oxygen evolution and reduction
CN104269278B (en) A kind of self-supporting nanoporous nickel nickel compound electric pole piece and preparation method thereof
CN106967997B (en) A kind of efficient self-supporting catalysis electrode and its preparation method and application
Jia et al. Understanding the growth of NiSe nanoparticles on reduced graphene oxide as efficient electrocatalysts for methanol oxidation reaction
CN106602092A (en) Preparation method for single-walled carbon nanotube (SWCNT) hollow ball oxygen reduction catalyst, and application of SWCNT hollow ball oxygen reduction catalyst
CN102380400B (en) Core-shell structural anode catalyst for direct borohydride fuel cells and preparation method thereof
CN100588018C (en) Preparation method for carbon supported ultra-low platinum catalytic electrode by indirect galvanic deposit
CN107863539B (en) Preparation method of biomass alkaline fuel cell anode
Guan et al. Synthesis of 3D flower-like nickel-molybdenum-sulfur microspheres as efficient and stable electrocatalyst for hydrogen and oxygen evolution reactions
CN104393307A (en) Carbon-free Ag-Cu catalyst layer-based air electrode and its making method
CN113363411B (en) Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery
CN100474670C (en) Method for producing carbon-carrying platinum-based alloy electrode
Ge et al. Electrocatalytic activity of cobalt phosphide-modified graphite felt toward VO2+/VO2+ redox reaction
Tang et al. Self-reconstruction of highly active NiCo2O4 with triple-continuous transfer of electrons, ions, and oxygen for Zn-air batteries
Liu et al. Preparation of three-dimensional porous Cu film supported on Cu foam and its electrocatalytic performance for hydrazine electrooxidation in alkaline medium
Liu et al. Porous 2D cobalt–nickel phosphide triangular nanowall architecture assembled by 3D microsphere for enhanced overall water splitting
Yin et al. High efficiency N/C foam supported Pd electrode for direct sodium borohydride-hydrogen peroxide fuel cell
CN104037428A (en) Direct methanol fuel cell with alloy-TiO2 nanotube/Ti anode and preparation method thereof
Du et al. Practical classification of catalysts for oxygen reduction reactions: Optimization strategies and mechanistic analysis
Shang et al. Oxygen vacancies boosted by laser irradiation enable NiCo layered double hydroxide with a high oxygen reduction/evolution catalytic activity in Zn–air batteries and water splitting
CN114045505B (en) High-activity large-size electrolysis water hydrogen evolution electrode and pulse laser preparation method thereof
Shi et al. Nanoporous bismuth electrocatalyst with high performance for glucose oxidation application
CN104319408B (en) Silver-copper nano alloy air-electrode catalyst layer and its deposition process

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant