CN110407577A - Ceramic membrane material, catalysis electrode and its preparation method and application - Google Patents

Ceramic membrane material, catalysis electrode and its preparation method and application Download PDF

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Publication number
CN110407577A
CN110407577A CN201910681627.0A CN201910681627A CN110407577A CN 110407577 A CN110407577 A CN 110407577A CN 201910681627 A CN201910681627 A CN 201910681627A CN 110407577 A CN110407577 A CN 110407577A
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zirconium
platinum
catalysis
compound
ceramic
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CN110407577B (en
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王田军
陈彬
胡延超
徐斌
李敏
苗伟峰
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Shenzhen Fuji New Material Technology Co Ltd
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HUIZHOU FUJI ELECTRONIC MATERIAL CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/3671—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electrodes
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Abstract

The present invention provides a kind of ceramic membrane material, catalysis electrode and its preparation method and application, catalysis electrode of the invention includes substrate and the ceramic film being carried on the substrate and the Catalytic Layer for being coated on the ceramic film.Catalysis electrode of the invention has good stability, catalytic activity and low cost of manufacture.Therefore solid fuel cell of the invention has good stability and energy conversion efficiency due to using the catalysis electrode.

Description

Ceramic membrane material, catalysis electrode and its preparation method and application
Technical field
The invention belongs to solid fuel cell fields, and in particular to a kind of catalysis electrode of solid fuel and preparation method thereof And application.
Background technique
Solid fuel cell (Solid Fuel Cell, abbreviation SFC) belongs to third generation fuel cell, is one kind in middle height The all solid state chemistry that the chemical energy being stored in fuel and oxidant directly efficiently, is environmentally friendly converted to electric energy under temperature is sent out Electric installation.Its high efficiency, pollution-free, structure of whole solid state and be that its is widely applied to extensive adaptability of pluralities of fuel gas etc. Basis.
Solid fuel cell chief component is by electrolyte (electrolyte), anode or fuel electrodes (anode, fuel Electrode), cathode or air pole (cathode, air electrode), catalysis electrode (Catalytic electrode) It is formed with connector (interconnect) or bipolar plates (bipolar separator).
The working principle of solid fuel cell, anode are the place that fuel aoxidizes, and cathode is the field of oxidant reduction The catalyst of reaction is learned by institute.A DC power supply, anode, that is, power cathode are equivalent to when work, cathode is positive pole.
It is continually fed into fuel gas in the anode side of solid fuel cell, such as: hydrogen (H2), methane (CH4), city coal Gas etc., the anode surface adsorbed fuel gas with catalytic action, and anode and electrolysis are diffused by the porous structure of anode The interface of matter.It is continually fed into oxygen or air in cathode side, the cathode surface with porous structure adsorbs oxygen, since cathode is urged The catalytic action of polarizing electrode, so that O2 obtains electronics and becomes O2-, under the action of chemical potential, O2- has entered electrolyte effect Solid oxygen ion conductor eventually arrives at the interface of solid electrolyte and anode since concentration gradient causes to spread, with fuel gas It reacts, the electronics lost returns to cathode by external circuit.
Fuel gas can enter from anode of fuel cell, resolve into cation and electronics through anode catalyst, later electronics Electric current can be formed via external circuit and arrive at cathode, after fuel gas loses electronics, then can pass through the cathode of electrolyte to next door O2-；Reaction is generated with the help of cathod catalyst forms water.
Above-mentioned characteristic allows hydrogen fuel cell to be considered as one of alternative energy source of fossil fuel, even more by good electric vehicle Power source, unfortunately, sufficiently expensive as the platinum of catalyst, at high cost and raw material is rare, can not be largely used to fuel Battery.Although scientist also want with other metals, alloy or compound that efficiency was all less than platinum come affected catalyst Gold.
Summary of the invention
The object of the present invention is to provide a kind of ceramic membrane materials, to solve existing ceramic membrane material as catalyst Supporting substrate specific surface area is not big enough, adsorption capacity is weak, activated catalyst ability is inadequate technical problem.
It is a further object of the present invention to provide a kind of catalysis electrodes and preparation method thereof, to solve existing catalysis electrode valence Lattice are expensive, stability and the inadequate technical problem of catalytic activity.
There is provided a kind of solid fuel cells for a further object of the present invention, to solve existing solid fuel cell cost Height, the technical problem that stability is insufficient, energy conversion efficiency is low.
In order to solve the above-mentioned technical problem one aspect of the present invention provides a kind of ceramic membrane material, including substrate and load Ceramic film on the substrate, the organic zirconium compound that the ceramic film is 10%-20% by mass fraction, Organic hafnium compound of 0.3%-2.8%, the yttrium of 1.0%-4.2%, the compound of cerium, 3%-5.5% carbon nano-fiber, The ceramic slurry that the pore creating material of 2.5%-8.0% and 70% organic solvent are configured to is made through sintering processes.
Preferably, the ceramic film with a thickness of 0.5-20um.
Preferably, the compound of the organic zirconium includes bicyclic pentadiene or bis- (methyl cyclopentadienyl) dichlorides Zirconium, zirconium iso-octoate, 2 ethyl hexanoic acid zirconium, bis cyclopentadienyl zirconium dichloride, tetrabenzyl zirconium four (ethylmethylamino) zirconium (IV), tetramethyl propylene Bis- [2- (2-[4-morpholinodithio base) phenol] the zinc zirconium-n-propylates of sour zirconium, hexafluoro-acetylacetone,2,4-pentanedione zirconium, bis- (the normal-butyl rings of acetylacetone,2,4-pentanedione zirconium Pentadienyl) zirconium dichloride, cyclopentadienyl group tri-chlorination zirconium, four (dimethylamino) zirconiums, 1.1.1.- trifluoroacetylacetone (TFA) zirconium, five In methyl cyclopentadienyl tri-chlorination zirconium (IV), tetraethoxy zirconium four (2,2,6,6- tetramethyl -3,5- pimelic acid) zirconium at least It is a kind of.
Preferably, organic hafnium compound include bicyclic pentadiene or bis- (methyl cyclopentadienyl) zirconium dichlorides, it is different Zirconium caprylate, 2 ethyl hexanoic acid zirconium, bis cyclopentadienyl zirconium dichloride, tetrabenzyl zirconium four (ethylmethylamino) zirconium (IV), acetylacetone,2,4-pentanedione hafnium, trifluoro At least one of Loprazolam hafnium (IV).
Preferably, the compound of the yttrium includes yttrium isopropoxide (III), trifluoromethanesulfonic acid yttrium (III), yttrium nitrate, (2,2, At least one of 6,6- tetramethyl -3,5- heptadione acid) yttrium.
Preferably, the compound of the cerium includes cerous carbonate (III), cerous nitrate, cerous acetate (III), cerium oxalate, fluoroform At least one of cerous iodate.
Preferably, the diameter of the carbon nano-fiber is 30-400nm, length 2um-500um；
Preferably, the pore creating material includes at least one of nano carbon black, PS micropowder, PMMA micropowder, described to make The micro-shape of hole agent is at least one of dendroid, spherical, sheet；The partial size of the pore creating material is 0.05um-10um.
Another aspect of the present invention provides a kind of catalysis electrode, including ceramic membrane material as mentioned and is coated on institute The Catalytic Layer on the ceramic film in ceramic membrane material is stated, the Catalytic Layer is 2.5%-18%'s by mass fraction The nano carbon black of organo-platinic compounds, 3.5%-20%, the organic adhesive of 4.5%-12%, the dispersing agent of 0.5%-2.0% The catalysis slurry being configured to the organic solvent of 35%-60% is obtained through sintering processes.
Preferably, the Catalytic Layer with a thickness of 0.02um-0.3um.
Preferably, the compound of the platinum includes the carbonyl complex of platinum, divinyl dichloro conjunction platinum, four ammino nitric acid Platinum, dinitroso diammonia platinum, bis- (benzonitrile) dichloro platinum (II), tetrachloro close four ammino platinate of platinum, bis- (tri-tert-butylphosphine) platinum (0), acetylacetone,2,4-pentanedione platinum (II), four (triphenylphosphine) platinum, cis- dichloro two (diethyl thioether) platinum (II), divinyl -1 1,3-, At least one of 1,3,3- tetramethyl disiloxane platinum (0).
The shape of the nano carbon black is at least one of dendroid, spherical, sheet；The partial size of the nano carbon black is 80nm-500nm。
Further aspect of the present invention provides a kind of preparation method of catalysis electrode, which comprises the steps of:
The organic zirconium compound for being 10%-20% by mass fraction, organic hafnium compound of 0.3%-2.8%, 1.0%-4.2% Yttrium, the compound of cerium, the carbon nano-fiber of 3%-5.5%, 2.5%-8.0% pore creating material be scattered in 70% organic solvent It is configured to ceramic slurry；
By slurry coating on the substrate, the ceramics for being carried on the substrate are obtained by drying, sintering processes Film layer；
By the nano carbon black of organo-platinic compounds, 3.5%-20% that mass fraction is 2.5%-18%, 4.5%-12% Organic adhesive, the dispersing agent of 0.5%-2.0% be scattered in mass fraction be 70% organic solvent be configured to catalysis slurry Material is carried on the ceramic film, obtains the catalysis electrode through drying, calcining, sintering processes.
Preferably, the sintering processes of the ceramic film are laser activation sintering processes.
Preferably, the mode of loading of the catalysis slurry is dip coating.
Preferably, the sintering processing of the catalysis slurry is microwave sintering.
Further aspect of the present invention provides a kind of solid fuel cell, including the catalysis electrode.
Compared with prior art, on the one hand ceramic membrane material of the present invention uses rare earth element to urge having auxiliary Change function zirconium oxide be doped, structural reform can the zirconium oxide electric conductivity, thermal stability and catalytic activity；Another aspect is adopted It is decomposed at high temperature with carbon nano-fiber and pore creating material, forms the void network structure of connection, improve porosity and specific surface area, Conducive to the circulation of gas with exchange；Another further aspect is sintered activation to ceramic surface using laser, promotes dilute in ceramics Doping of the earth elements to zirconia material, activation ceramic grain surface are conducive in conjunction with subsequent catalyst layer.Generally speaking improve Electric conductivity, stability and auxiliary catalysis ability of this ceramic material as catalysis support materials.
On the one hand catalysis electrode of the invention is based on the ceramic membrane material, so that the catalysis electrode, which has, compares table Area is big, stability, good conductivity, is also equipped with good catalytic activity.On the other hand first using dip-coating in surface layer overlay Then Catalytic Layer makes ultra-fine platinum grain in conjunction with ceramic surface, and refines the crystal grain of platinum grain by Fast Sintering, and protect Nascent state platinum surface-active is held, catalytic activity is further promoted.Finally due to largely using auxiliary catalysis material, and pass through technique It improves, greatly reduces the dosage of noble metal platinum, greatly reduce cost.
The preparation method of catalysis electrode of the invention is high-efficient, at low cost, and the catalysis electrode function of preparing is excellent.
Therefore solid fuel cell of the invention has good stability and energy due to using the catalysis electrode Transformation efficiency.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of catalysis electrode described in one embodiment of the invention.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain The present invention is not intended to limit the present invention.
On the one hand the embodiment of the present invention provides a kind of pottery for having porous structure and having certain auxiliary catalysis ability Porcelain thin-film material, including substrate and the ceramic film being carried on the substrate, the ceramic film is by mass fraction The organic zirconium compound of 10%-20%, organic hafnium compound of 0.3%-2.8%, the yttrium of 1.0%-4.2%, the compound of cerium, 3%- 5.5% carbon nano-fiber, the pore creating material of 2.5%-8.0% and 70% the ceramic slurry that is configured to of organic solvent through sintering at Reason is made.
The specific substrate is using conventional ceramics or glass material, using organic zirconium compound as raw material, sintering Zirconium oxide is formed, has certain catalytic capability, while adulterating these rare-earth oxides of hafnium, yttrium, cerium, improves zirconia powder Ionic conductivity, thermal stability and the catalytic activity of last particle.More specifically, the ceramic film in a preferred embodiment With a thickness of 0.5-20um.It is that slurry is used to form coating, therefore the thickness generated on substrate when preparing ceramic film Will not too uniformly, but ceramic membrane of the invention does not need uniform thickness.The organic zirconium in another preferred embodiment Compound include bicyclic pentadiene or bis- (methyl cyclopentadienyl) zirconium dichlorides, zirconium iso-octoate, 2 ethyl hexanoic acid zirconium, two Bis- [2- (2-[4-morpholinodithio base) benzene of chlorine zirconocene, tetrabenzyl zirconium four (ethylmethylamino) zirconium (IV), tetramethyl acrylic acid zirconium Phenol] zinc zirconium-n-propylate, hexafluoro-acetylacetone,2,4-pentanedione zirconium, bis- (n-butyl cyclopentadienyl) zirconium dichlorides of acetylacetone,2,4-pentanedione zirconium, cyclopentadiene Base tri-chlorination zirconium, four (dimethylamino) zirconiums, 1.1.1.- trifluoroacetylacetone (TFA) zirconium, pentamethylcyclopentadiene base tri-chlorination zirconium (IV), At least one of tetraethoxy zirconium four (2,2,6,6- tetramethyl -3,5- pimelic acid) zirconium.Organic zirconium compound is selected, is on the one hand Material base is provided to form zirconium oxide after sintering, another aspect organic ligand is oxidized into gas after high temperature sintering, Expansion forms porous structure in system.The dosage of carbon fiber and pore creating material in system can be reduced.In another aspect, the zirconium The zirconium oxide that compound is formed has co-catalysis effect, can effectively reduce the dosage of platinum.It is described in another preferred embodiment Organic hafnium compound include bicyclic pentadiene or bis- (methyl cyclopentadienyl) zirconium dichlorides, zirconium iso-octoate, 2 ethyl hexanoic acid zirconium, Bis cyclopentadienyl zirconium dichloride, tetrabenzyl zirconium four (ethylmethylamino) zirconium (IV), acetylacetone,2,4-pentanedione hafnium, in trifluoromethayl sulfonic acid hafnium (IV) extremely Few one kind.In a further preferred embodiment, the compound of the yttrium includes yttrium isopropoxide (III), trifluoromethanesulfonic acid yttrium (III), Yttrium nitrate, at least one of (2,2,6,6- tetramethyl -3,5- heptadione acid) yttrium.In a further preferred embodiment, the cerium Compound include at least one of cerous carbonate (III), cerous nitrate, cerous acetate (III), cerium oxalate, trifluoromethanesulfonic acid cerium.
Other than the carbon of ligand itself institute band or other elements generate gas, it is also necessary to supplement carbon and guarantee enough Carbon source generate enough carbon dioxide gas, form the void network structure of connection, improve porosity and specific surface area, be conducive to The circulation of gas with exchange.In a preferred embodiment, the diameter of the carbon nano-fiber is 30-400nm, length 2um- 500um；The pore creating material is including being at least one of nano carbon black, PS micropowder, PMMA micropowder, the grain of the pore creating material Diameter is 0.05um-10um；Subtle Nano carbon fibers peacekeeping pore creating material powder is easier to be oxidized to gas and form hole, therefore Choose this particle size range.
On the other hand the embodiment of the present invention provides a kind of catalysis electrode based on the ceramic membrane material.The catalysis Electrode includes urging on the ceramic membrane material and the ceramic film being coated in the ceramic membrane material Change layer, catalysis electrode described in the embodiment of the present invention has porous structure, is as shown in Figure 1 the porous structure of one embodiment of the invention The scanning electron microscope (SEM) photograph of catalysis electrode.Organo-platinic compounds, the 3.5%- that the Catalytic Layer is 2.5%-18% by mass fraction 20% nano carbon black, the organic adhesive of 4.5%-12%, the dispersing agent of 0.5%-2.0% and 70% organic solvent configuration At catalysis slurry obtained through sintering processes.Dispersing agent helps the catalyst being tentatively uniformly dispersed, described in bonding agent help Preliminary Nian Jie with the ceramic film of catalyst.The ligand and bonding agent of the nano carbon black and organic platinum, dispersing agent It is carbonized to form air-flow during the sintering process, on the one hand can form porous structure, after on the other hand other ingredients become gas, It forms platinum directly to contact with the ceramic film, interact, form catalyst system.In a preferred embodiment, described Catalytic Layer with a thickness of 0.02um-0.3um.In gas-solid phase reaction, the amount that the catalyst of contact needs is seldom, it is only necessary to very Thin one layer can be made ultra-thin, but is limited to process conditions, preferably this thickness range theoretically for raw material is saved.Another In one preferred embodiment, the compound of the platinum includes the carbonyl complex of platinum, divinyl dichloro conjunction platinum, four ammino nitric acid Platinum, dinitroso diammonia platinum, bis- (benzonitrile) dichloro platinum (II), tetrachloro close four ammino platinate of platinum, bis- (tri-tert-butylphosphine) platinum (0), acetylacetone,2,4-pentanedione platinum (II), four (triphenylphosphine) platinum, cis- dichloro two (diethyl thioether) platinum (II), divinyl -1 1,3-, At least one of 1,3,3- tetramethyl disiloxane platinum (0).In a further preferred embodiment, the shape of the nano carbon black is At least one of dendroid, spherical, flake shape；The partial size of the nano carbon black is that the partial size of the nano carbon black is 80nm-500nm.Carbon black purposes is to form the raw material of gas not carrying repeated description technical effect as aforementioned herein.
On the one hand the embodiment of the present invention also provides a kind of preparation method of catalysis electrode, which is characterized in that including as follows Step:
S01: the organic zirconium compound for being 10%-20% by mass fraction, organic hafnium compound of 0.3%-2.8%, 1.0%- 4.2% yttrium, the compound of cerium, the carbon nano-fiber of 3%-5.5%, 2.5%-8.0% nano carbon black be scattered in 70% Organic solvent is configured to ceramic slurry；
S02: it by slurry coating on the substrate, obtains being carried on the substrate by drying, sintering processes Ceramic film；
S03: by the nano carbon black of organo-platinic compounds, 3.5%-20% that mass fraction is 2.5%-18%, 4.5%- 12% organic adhesive, the dispersing agent of 0.5%-2.0% are scattered in the urging of being configured to of organic solvent that mass fraction is 70% Slurrying material is carried on the ceramic film, obtains the catalysis electrode through drying, calcining, sintering processes.
Specifically in step S01, the organic solvent of use include dehydrated alcohol, DBE, methyl carbonate, ethyl acetate, One of NMP or a variety of.
Specifically in step S02, drying process is first passed through, then may also pass through calcination processing, it is mild to go out one Part volatile substances finally form ceramic film by sintering processes.The sintering processes of the ceramic film are laser Activated sintering processing.On the one hand laser, which has higher energy, can provide sintering required high temperature, on the other hand can also activate institute State the co-catalysis performance of zirconia system.
Specifically in step S03, the mode of loading of the catalysis slurry is dip coating.The ceramic thin of the embodiment of the present invention Film has formd porous structure, using the bad covering of coating method, cannot utilize ceramic membrane load matrix well Big specific surface area, and may be implemented to cover comprehensively using dip coating, and the concentration for controlling slurry also can control Catalytic Layer Thickness, be allowed to it is adjustable achieve the purpose that reduce noble metal platinum dosage with save the cost.
Specifically in step S03, the sintering processing of the catalysis slurry is microwave sintering.In microwave agglomerating furnace into Row Fast Sintering, inside and outside while heating advantage, so that ultra-fine platinum grain and ceramic surface fast using microwave sintering heating rate In conjunction with, and the crystal grain of platinum grain is refined, and keep nascent state platinum surface-active.
Another further aspect of the embodiment of the present invention provides a kind of solid fuel cell, including the catalysis electrode.Therefore it inherits The advantages of catalysis electrode.On the one hand have the good stability of ceramic membrane material bring, and reach specific surface area band Come catalysis area and the rare earth doped oxide of zirconium oxide bring catalytic activity integrate electrochemical reaction activity.So Afterwards plus platinum in the superior catalytic performance on surface, so that the solid fuel cell stability is good, electric property is good, that is, most Big voltage is big, and energy conversion efficiency is high.
Embodiment 1
A kind of ceramic membrane material is present embodiments provided to prepare using following methods:
By mass fraction be 10% bicyclic pentadiene or bis- (methyl cyclopentadienyl) zirconium dichlorides, 2.8% it is different Sad hafnium；1.0% yttrium nitrate, 1.0% cerium oxalate, 5.5% carbon fiber, 2.5% nano carbon black and PS micropowder point It dissipates and carries out the dispersion of abundant ball milling in the methyl carbonate of surplus percentage ceramic slurry is made；
The ceramic slurry is coated on substrate, is dried at 120 DEG C, then with 3 DEG C of heating rate to 900 DEG C, heating and calcining is carried out with air atmosphere in chamber type sintering furnace, keeps the temperature 0.5h, finally is sintered to obtain porcelain by laser activation Thin-film material.
The present embodiment additionally provides a kind of catalysis electrode, and on the basis of above-mentioned ceramic membrane material prepared by following methods:
The divinyl dichloro that mass fraction is 3% is closed into platinum, 4% nano carbon black, 8% organic adhesive, 1% The abundant ball milling of dispersing agent, which is scattered in the methyl carbonate of surplus percentage, is made catalysis slurry；The preparation process of the slurry be by Various composition is put into glass and is sufficiently stirred by ratio, is then placed in contactless planet stirring vacuum defoamation all-in-one machine, According to 3 low speed dispersion stirring, high speed dispersion stirring, vacuum defoamation step preparations.Supplemental characteristic are as follows: contactless planetary to stir Vacuum degree-the 0.095MPa for mixing vacuum defoamation all-in-one machine, when stirring at low speed, revolution revolving speed is 60r/min, revolution with from revolving speed The ratio between degree is 1:1；When high-speed stirred, revolution revolving speed is 1000r/min, and the ratio between revolution and rotational velocity are 2:1.At dispersion In slurry dip-coating and the thin layers of ceramic material after reason, 3 hours are dried at 120 DEG C, then with 3 DEG C of heating rate To 600 DEG C, heating and calcining is carried out with air atmosphere in chamber type sintering furnace, keeps the temperature 0.5-2h, then uses and is transferred to microwave burning Fast Sintering is carried out in freezing of a furnace, sintering temperature is 900 DEG C, and the microwave sintering time is that 60min obtains the catalysis electrode.
Embodiment 2
A kind of ceramic membrane material is present embodiments provided to prepare using following methods:
It is 20% zirconium iso-octoate, 0.3% isooctyl acid hafnium by mass fraction；2.1% yttrium isopropoxide (III), 2.1% Cerous carbonate (III), 3% carbon fiber, 8% PMMA micropowder be scattered in the methyl carbonate of surplus percentage carry out it is abundant Ceramic slurry is made in ball milling dispersion；
The ceramic slurry is coated on substrate, is dried at 120 DEG C, then with 3 DEG C of heating rate to 900 DEG C, heating and calcining is carried out with air atmosphere in chamber type sintering furnace, keeps the temperature 2h, finally is sintered to obtain porcelain by laser activation thin Membrane material.
The present embodiment additionally provides a kind of catalysis electrode, and on the basis of above-mentioned ceramic membrane material prepared by following methods:
By mass fraction be 18% dinitroso diammonia platinum, 3.5% nano carbon black, 12% organic adhesive, 2% The abundant ball milling of dispersing agent be scattered in the methyl carbonate of surplus percentage catalysis slurry be made；The preparation process of the slurry is Various composition is put into glass in proportion and is sufficiently stirred, contactless planet stirring vacuum defoamation all-in-one machine is then placed in In, according to 3 low speed dispersion stirring, high speed dispersion stirring, vacuum defoamation step preparations.Supplemental characteristic are as follows: contactless planet Vacuum degree-the 0.095MPa of formula stirring vacuum deaeration all-in-one machine, when stirring at low speed, revolution revolving speed be 100r/min, revolution with The ratio between rotational velocity is 1:1；When high-speed stirred, revolution revolving speed is 600r/min, and the ratio between revolution and rotational velocity are 1:1.It will In slurry dip-coating and the thin layers of ceramic material after decentralized processing, 3 hours are dried at 120 DEG C, then with 3 DEG C of liter Warm speed carries out heating and calcining in chamber type sintering furnace to 600 DEG C with air atmosphere, keeps the temperature 2h, then uses and is transferred to microwave Fast Sintering is carried out in sintering furnace, sintering temperature is 900 DEG C, and the microwave sintering time is that 20min obtains the catalysis electrode.
Embodiment 3
A kind of ceramic membrane material is present embodiments provided to prepare using following methods:
The cyclopentadienyl group tri-chlorination zirconium and the bis- [2- (2-[4-morpholinodithios of tetramethyl acrylic acid zirconium for being 16% by mass fraction Base) phenol] zinc zirconium-n-propylate, 2.8% isooctyl acid hafnium, tetrabenzyl zirconium four (ethylmethylamino) zirconium (IV) and fluoroform sulphur Sour hafnium (IV)；1.4% (DPM dpm,dipivalomethane acid) yttrium, 0.8% cerium oxalate and trifluoromethanesulfonic acid cerium, 5.5% carbon fiber, PS micropowder, which are scattered in the ethyl alcohol of surplus percentage, to carry out abundant ball milling dispersion ceramic slurry is made；
The ceramic slurry is coated on substrate, is dried at 120 DEG C, then with 3 DEG C of heating rate to 900 DEG C, heating and calcining is carried out with air atmosphere in chamber type sintering furnace, keeps the temperature 1.5h, finally is sintered to obtain porcelain by laser activation Thin-film material.
The present embodiment additionally provides a kind of catalysis electrode, and on the basis of above-mentioned ceramic membrane material prepared by following methods:
The divinyl dichloro that mass fraction is 10% is closed into platinum, acetylacetone,2,4-pentanedione platinum (II), four (triphenylphosphine) platinum and cis- Dichloro two (diethyl thioether) platinum (II), 19% nano carbon black, 12% organic adhesive, 2% the abundant ball milling of dispersing agent It is scattered in the ethyl alcohol of surplus percentage and catalysis slurry is made；The preparation process of the slurry is in proportion to be put into various composition It is sufficiently stirred, is then placed in contactless planet stirring vacuum defoamation all-in-one machine in glass, according to low speed dispersion stirring, height 3 speed dispersion stirring, vacuum defoamation step preparations.Supplemental characteristic are as follows: contactless planetary stirring vacuum deaeration all-in-one machine Vacuum degree -0.095MPa, when stirring at low speed, revolution revolving speed is 200r/min, and the ratio between revolution and rotational velocity are 5:1；At a high speed When stirring, revolution revolving speed is 2000r/min, and the ratio between revolution and rotational velocity are 6:1.By after decentralized processing slurry dip-coating with On the thin layers of ceramic material, 3 hours are dried at 120 DEG C, then with 3 DEG C of heating rate to 600 DEG C, in box burning Heating and calcining is carried out with air atmosphere in freezing of a furnace, keeps the temperature 2h, then carries out Fast Sintering using being transferred in microwave agglomerating furnace, Sintering temperature is 200 DEG C, and the microwave sintering time is that 120min obtains the catalysis electrode.
Embodiment 4
A kind of ceramic membrane material is present embodiments provided to prepare using following methods:
Cyclopentadienyl group tri-chlorination zirconium, four (dimethylamino) zirconiums, 1.1.1.- trifluoroacetyl third by mass fraction for 20% Ketone zirconium and pentamethylcyclopentadiene base tri-chlorination zirconium (IV), 1.8% bis cyclopentadienyl zirconium dichloride, tetrabenzyl zirconium four (ethylmethylamino) Zirconium (IV), acetylacetone,2,4-pentanedione hafnium and trifluoromethayl sulfonic acid hafnium (IV)；2.0% yttrium isopropoxide (III) and trifluoromethanesulfonic acid yttrium (III), 0.5% cerium oxalate, 5.5% carbon fiber, 2.5% nano carbon black, PS micropowder and PMMA micropowder are scattered in Abundant ball milling dispersion is carried out in the mixed solvent (solvent ratios 2:3) of the DBE and NMP of surplus percentage, and ceramic slurry is made；
The ceramic slurry is coated on substrate, is dried at 120 DEG C, then with 3 DEG C of heating rate to 900 DEG C, heating and calcining is carried out with air atmosphere in chamber type sintering furnace, keeps the temperature 0.5h, finally is sintered to obtain porcelain by laser activation Thin-film material.
The present embodiment additionally provides a kind of catalysis electrode, and on the basis of above-mentioned ceramic membrane material prepared by following methods:
By mass fraction be 2.5% four (triphenylphosphine) platinum, 12% nano carbon black, 12% organic adhesive, The abundant ball milling of 1.6% dispersing agent be scattered in surplus percentage DBE, ethyl acetate and NMP mixed solvent (solvent ratios 1: Catalysis slurry is made in 2:3)；The preparation process of the slurry is various composition to be put into glass to be sufficiently stirred in proportion, It is then placed in contactless planet stirring vacuum defoamation all-in-one machine, it is de- according to low speed dispersion stirring, high speed dispersion stirring, vacuum Steep 3 step preparations.Supplemental characteristic are as follows: the vacuum degree -0.095MPa of contactless planetary stirring vacuum deaeration all-in-one machine is low When speed stirring, revolution revolving speed is 200r/min, and the ratio between revolution and rotational velocity are 1:1；When high-speed stirred, revolution revolving speed is 1000r/min, the ratio between revolution and rotational velocity are 3:1.By after decentralized processing slurry dip-coating and the thin layers of ceramic material on, 3 hours are dried at 120 DEG C, then with 3 DEG C of heating rate to 600 DEG C, with air atmosphere in chamber type sintering furnace Heating and calcining is carried out, 1.1h is kept the temperature, then use, which is transferred in microwave agglomerating furnace, carries out Fast Sintering, sintering temperature 1100 DEG C, the microwave sintering time is that 60min obtains the catalysis electrode.
Embodiment 5
A kind of ceramic membrane material is present embodiments provided to prepare using following methods:
It is 18% zirconium iso-octoate and 2 ethyl hexanoic acid zirconium by mass fraction, 0.8% acetylacetone,2,4-pentanedione hafnium and fluoroform Sulfonic acid hafnium (IV)；1.0% yttrium nitrate, 2.2% trifluoromethanesulfonic acid cerium, 4% carbon fiber, 8% nano carbon black be scattered in Abundant ball milling dispersion is carried out in the methyl carbonate of surplus percentage, and ceramic slurry is made；
The ceramic slurry is coated on substrate, is dried at 120 DEG C, then with 3 DEG C of heating rate to 900 DEG C, heating and calcining is carried out with air atmosphere in chamber type sintering furnace, keeps the temperature 2h, finally is sintered to obtain porcelain by laser activation thin Membrane material.
The present embodiment additionally provides a kind of catalysis electrode, and on the basis of above-mentioned ceramic membrane material prepared by following methods:
By mass fraction be 6% four ammino platinum nitrates, 20% nano carbon black, 6% organic adhesive, 1.2% The abundant ball milling of dispersing agent, which is scattered in the ethyl alcohol of surplus percentage, is made catalysis slurry；The preparation process of the slurry is in proportion Various composition is put into glass and is sufficiently stirred, is then placed in contactless planet stirring vacuum defoamation all-in-one machine, according to 3 low speed dispersion stirring, high speed dispersion stirring, vacuum defoamation step preparations.Supplemental characteristic are as follows: contactless planetary stirring is true Vacuum degree-the 0.095MPa of empty deaeration all-in-one machine, when stirring at low speed, revolution revolving speed be 40r/min, revolution with rotational velocity it Than for 1:3；When high-speed stirred, revolution revolving speed is 360r/min, and the ratio between revolution and rotational velocity are 4:1.After decentralized processing Slurry dip-coating and the thin layers of ceramic material on, 3 hours are dried at 120 DEG C, are then arrived with 3 DEG C of heating rate 600 DEG C, heating and calcining is carried out with air atmosphere in chamber type sintering furnace, keeps the temperature 1.5h, then uses and is transferred to microwave agglomerating furnace Fast Sintering is carried out in the middle, and sintering temperature is 950 DEG C, and the microwave sintering time is that 70min obtains the catalysis electrode.
Performance test to the catalysis electrode of embodiment 1-5:
Testing performance index method: elctro-catalyst test method (GB/T 20042.4-2009)
1. test Pt content measuring data are 0.06-0.1mg/cm2Catalysis electrode exactly every square centimeter contains 0.06-0.1 milligrams of platinum.Traditional Pt/C catalysis electrode is 0.3-0.6mg/cm2。
2. electrochemical surface area (ECA) is tested: 53.6-61.2m2/g。
3. electrode catalyst performance: 550-650mA/cm2, it is 2 times of traditional Pt/C catalysis electrode.
4. power density: test data is that 2-3kw/g Pt is exactly the power that every gram of platinum of fuel cell can produce 3kw.It passes The Pt/C catalysis electrode of system is 0.4-0.73kw/g Pt
5. stability test: by 20000 circle accelerated ageing loop tests, electrochemical surface area attenuation rate is lower than 15%.Electrode catalyst performance degradation rate is lower than 20%.
It can be seen that less noble metal platinum can be used using catalysis electrode prepared by this method, cost is saved, and described The properties of catalysis electrode all do not reduce or even some performances are also obtained and are obviously improved.
The performance data of specific embodiment 1-5 is as follows:
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Pt content mg/cm2 0.063 0.103 0.081 0.059 0.075
Electrochemical surface area m2/g 60.3 53.6 58.1 61.2 59.2
Electrocatalysis characteristic mA/cm2 563 657 609 555 583
Power density kw/g Pt 2.13 3.01 2.33 2.04 2.21
Electrochemical surface area attenuation rate 10.60% 14.70% 9.80% 11.90% 13.50%
Electrode catalyst performance degradation rate 12.30% 19.30% 15.10% 16.60% 17.70%

Claims (10)

1. a kind of ceramic membrane material, including substrate and the ceramic film being carried on the substrate, it is characterised in that: described The organic zirconium compound that ceramic film is 10%-20% by mass fraction, organic hafnium compound of 0.3%-2.8%, 1.0%- 4.2% yttrium, the compound of cerium, the carbon nano-fiber of 3%-5.5%, the pore creating material of 2.5%-8.0% and 70% it is organic molten The ceramic slurry sintering processes that agent is configured to are made.
2. ceramic membrane material as described in claim 1, it is characterised in that: the ceramic film with a thickness of 0.5- 20um。
3. ceramic membrane material as described in claim 1, it is characterised in that: the compound of the organic zirconium includes bicyclic penta 2 Alkenyl or bis- (methyl cyclopentadienyl) zirconium dichlorides, zirconium iso-octoate, 2 ethyl hexanoic acid zirconium, bis cyclopentadienyl zirconium dichloride, tetrabenzyl zirconium four (ethylmethylamino) zirconium (IV), tetramethyl acrylic acid zirconium bis- [2- (2-[4-morpholinodithio base) phenol] zinc zirconium-n-propylates, hexafluoro-second Bis- (n-butyl cyclopentadienyl) zirconium dichlorides of acyl acetone zirconium, acetylacetone,2,4-pentanedione zirconium, cyclopentadienyl group tri-chlorination zirconium, four (diformazan ammonia Base) zirconium, 1.1.1.- trifluoroacetylacetone (TFA) zirconium, pentamethylcyclopentadiene base tri-chlorination zirconium (IV), tetraethoxy zirconium four (2,2,6, At least one of 6- tetramethyl -3,5- pimelic acid) zirconium；And/or
Organic hafnium compound includes bicyclic pentadiene or bis- (methyl cyclopentadienyl) zirconium dichlorides, zirconium iso-octoate, 2- second Base zirconium hexanoate, bis cyclopentadienyl zirconium dichloride, tetrabenzyl zirconium four (ethylmethylamino) zirconium (IV), acetylacetone,2,4-pentanedione hafnium, trifluoromethayl sulfonic acid hafnium At least one of (IV)；And/or
The compound of the yttrium includes yttrium isopropoxide (III), trifluoromethanesulfonic acid yttrium (III), yttrium nitrate, (2,2,6,6- tetramethyls- At least one of 3,5- heptadione acid) yttrium；And/or
The compound of the cerium include cerous carbonate (III), cerous nitrate, cerous acetate (III), cerium oxalate, in trifluoromethanesulfonic acid cerium It is at least one；And/or
The diameter of the carbon nano-fiber is 30-400nm, length 2um-500um；And/or
The pore creating material includes at least one of nano carbon black, PS micropowder, PMMA micropowder, the microcosmic shape of the pore creating material Shape is at least one of dendroid, spherical, sheet；The partial size of the pore creating material is 0.05um-10um.
4. a kind of catalysis electrode, including ceramic membrane material a method according to any one of claims 1-3 and it is coated on the ceramics The Catalytic Layer on the ceramic film in thin-film material, it is characterised in that: the Catalytic Layer is 2.5%- by mass fraction The nano carbon black of 18% organo-platinic compounds, 3.5%-20%, the organic adhesive of 4.5%-12%, 0.5%-2.0%'s Dispersing agent and the 70% catalysis slurry that is configured to of organic solvent are obtained through sintering processes.
5. catalysis electrode as claimed in claim 4, it is characterised in that: the Catalytic Layer with a thickness of 0.02um-0.3um.
6. catalysis electrode as claimed in claim 4, it is characterised in that: the compound of the platinum include the carbonyl complex of platinum, Divinyl dichloro closes platinum, four ammino platinum nitrates, dinitroso diammonia platinum, bis- (benzonitrile) dichloro platinum (II), tetrachloro conjunction four ammonia of platinum Close platinate, bis- (tri-tert-butylphosphine) platinum (0), acetylacetone,2,4-pentanedione platinum (II), four (triphenylphosphine) platinum, two (diethyl sulfide of cis- dichloro Ether) platinum (II), at least one of 1,3- divinyl -1,1,3,3- tetramethyl disiloxane platinum (0)；And/or
The shape of the nano carbon black is at least one of dendroid, spherical, sheet；The partial size of the nano carbon black is 80nm-500nm。
7. a kind of preparation method of catalysis electrode, which comprises the steps of:
The organic zirconium compound for being 10%-20% by mass fraction, organic hafnium compound of 0.3%-2.8%, 1.0%-4.2%'s Yttrium, the compound of cerium, the carbon nano-fiber of 3%-5.5%, 2.5%-8.0% nano carbon black be scattered in 70% organic solvent It is configured to ceramic slurry；
By slurry coating on the substrate, the ceramics for being carried on the substrate are obtained by drying, calcining, sintering processes Film layer；
By the nano carbon black of organo-platinic compounds, 3.5%-20% that mass fraction is 2.5%-18%, 4.5%-12%'s has Machine bonding agent, the dispersing agent of 0.5%-2.0% are scattered in the catalysis slurry that the organic solvent that mass fraction is 35%-60% is configured to Material is carried on the ceramic film, obtains the catalysis electrode through drying, calcining, sintering processes.
8. the preparation method of catalysis electrode as claimed in claim 7, it is characterised in that: the sintering processes of the ceramic film For laser activation sintering processes.
9. the preparation method of catalysis electrode as claimed in claim 7, it is characterised in that: it is described catalysis slurry mode of loading be Dip coating；
The sintering processing of the catalysis slurry is microwave sintering.
10. a kind of solid fuel cell, it is characterised in that: including any catalysis electrode of claim 4-6.
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