CN102306810A - Composite catalyst of self-humidifying fuel cell and manufacturing method and application thereof - Google Patents
Composite catalyst of self-humidifying fuel cell and manufacturing method and application thereof Download PDFInfo
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Abstract
The invention provides a composite catalyst of a self-humidifying fuel cell and a manufacturing method and application thereof. The composite catalyst is prepared by depositing water-retaining substance and metallic oxide together on a carbon carrier to obtain a composite carrier, and then bearing noble metal on the composite carrier by using a high-pressure organosol method or microwave-aided high-pressure organosol method. The water-retaining substance is silicon dioxide, titanium dioxide or tungsten trioxide, the metallic oxide is ruthenium oxide or iridium oxide, and the noble metal is platinum, platinum ruthenium or platinum palladium. In the invention, by adding the metallic oxide, the performance of the catalyst can be improved effectively; the catalyst is used directly, and a membrane electrode is manufactured by a spray coating method which not only can obtain a membrane electrode with good moisture retention, but also improves the performance of the membrane electrode by over 20% in comparison with the membrane electrode manufactured by using the catalyst without metallic oxide. The manufacturing method provided by the invention is simple, does not need special equipment and can realize large-scale production of the catalysts.
Description
Technical field
The present invention relates to the eelctro-catalyst of fuel cell, particularly relate to self-humidifying fuel cell composite catalyst and preparation method thereof and application.
Background technology
The water management of Proton Exchange Membrane Fuel Cells (PEMFC) has become one of hot subject of fuel cell studies.During the PEMFC operation; In order to make membrane electrode (MEA) keep higher proton conductivity; Usually need carry out extra humidification to reacting gas, and the humidifying equipment that brings thus increases the cost and the complexity of fuel cell system, and brought extra energy consumption.In fact, the PEMFC negative electrode that is in operation can produce a large amount of water, and therefore, thereby some researchers hope these water conservancies are used and realize from humidification or exempt from the membrane electrode and the corresponding fuel cell system of humidification.
At present; The research of self-humidifying fuel cell mainly concentrates on the following aspects: 1) from the humidification composite membrane; Through changing the electrolytical microstructure of conventional solid; The reacting gas that is penetrated in the film is reacted; Generate water moistening self; Or, come the water holding capacity of reinforcing membrane self through adding the hydrophilic oxide particle; 2),, or between Catalytic Layer and film or diffusion layer, construct the layer of preserving moisture and reach effect from humidification mainly through in anode catalyst layer, mixing hydroaropic substance from the humidification Catalytic Layer; 3) other design from humidification, like the water that the particular design that relies on stream field or diffusion layer keeps and utilizes the cathode side electrochemical reaction to generate, strengthen the retrodiffusion of water anode side and the water holding capacity of MEA, reach the purpose from humidification.Regrettably, up to the present, it is desirable from humidification or exempt from the effect of humidification that these methods all can not reach in practical application.
Chinese patent ZL02122635.0 discloses " a kind of preparation method of self-humidifying composite proton exchange film for fuel cell "; This patent application is the heating for dissolving perfluoro sulfonic acid membrane in the solvent of the organic alcohol and water of low boiling; Process perfluor sulfoacid resin solution; In perfluor sulfoacid resin solution, add supported catalyst and the high boiling organic solvent that contains Pt then; Drips of solution is added in the surface of perforated membrane, and heating and vacuum are preserved and are promptly made from the humidification composite membrane.Therefore and be not suitable for practical application this method adds catalyst in film, cause short circuit easily, and the interpolation of non-proton conductor carrier, and the internal resistance that can increase film reduces battery performance.
Chinese patent ZL200610134014.8 discloses " a kind of self-humidifying fuel cell is with compound proton exchange membrane and synthesis method thereof "; This patent is distributed to supported catalyst in the organic solution of polymer solid electrolyte and forms casting solution; Adopt cast, spraying or casting method to be filled in the porous reinforcing membrane then and be prepared into self-humidifying composite proton exchange film, but adopt the self-humidifying composite proton exchange film conductivity of this method preparation lower.
People such as Zhang (Zhang W.J.; Yue P.L.; Gao P. Langmuir; 2008; 24 (6): 2663-2670.) through a kind of novel chemical vapour deposition technique; The Pt nano particle that will have high-crystallinity deposits to a kind of surface of hydrophily limellar stripping type nano imvite, again through the double teeming method, makes a kind of novel Pt-clay/Nafion nano composite membrane.At H
2And O
2Fully not under the humidified condition, battery performance test shows that this novel Pt-clay/Nafion reaches 723 mWcm from the power density of humidification composite membrane during at 0.5 V
-2This method exists the introducing of preparation trouble, Pt to cause the generation of short circuit current easily, exempts from the shortcoming that the humidification effect can not reach long-term stability.
Chinese patent ZL200510037575.1 discloses " a kind of self-humidifying membrane electrode and preparation method thereof "; This method is with the proton exchange membrane preliminary treatment; Carbon supported platinum catalyst, perfluorinated sulfonic acid polymer, hydroaropic substance and low boiling point solvent mix; Be coated in a side of proton exchange membrane, oven dry makes the hydrophily hydrogen electrode; Carbon supported platinum catalyst, perfluorinated sulfonic acid polymer, lyophobic dust and low boiling point solvent are mixed again, be coated in the opposite side of proton exchange membrane, oven dry makes the hydrophobicity oxygen electrode; Two carbon papers are fitted into self-humidifying membrane electrode with proton exchange membrane.With similar from the humidification composite membrane, stability also is the problem that need pay close attention to from the humidification Catalytic Layer.Because hydrophilic particle just simply mixes, rather than is fixed in the Catalytic Layer, therefore, membrane electrode runs off easily or reunion when working, and this has just reduced the long-term operation performance of fuel cell.In addition; Simply mix these and do not lead the proton oxide particle of non-conductive son again; The conductivity and the reduction Catalytic Layer that also can reduce entire electrode contact with interface between the film, and the employed hydrophily of this patent and hydrophobicity material can increase the charge transfer resistance of Catalytic Layer.
Chinese patent ZL200910041374.7 discloses " eelctro-catalyst that is used for fuel cell membrane electrode with and preparation method thereof and fuel cell membrane electrode "; This patent application is that the carbon carrier with the water-retaining property electrodeposition substance is a complex carrier; On complex carrier, support noble metal again and be prepared into eelctro-catalyst, and be that anode preparation becomes fuel cell membrane electrode in order to catalyst.This method is because the deposition of water-retaining property material on carbon carrier makes the conductance of Catalytic Layer reduce.
Chinese patent ZL200910188222.X discloses " catalyst coated membrane electrode of fuel cell and preparation method with self-moistening function "; In this patent; The catalyst coat of proton exchange membrane both sides has interior outer double-layer structure; The catalyst coat of pressing close to proton exchange membrane is an inner catalyst layer, and the content from humidizer and proton exchange resins in this Catalytic Layer is high; The catalyst coat of pressing close to gas diffusion layers is outer catalyst layer, and the content from humidizer and proton exchange resins in the outer catalyst layer is low, and the Pt loading of inside and outside catalyst layer is identical.This method prepares numerous and diverse, and two-layer Catalytic Layer can increase the charge transfer resistance of Catalytic Layer.
Chinese patent ZL200610015663.6 discloses " a kind of preparation method of self-humidifying proton exchange film fuel cell membrane electrode "; This patent application forms the constant humidity layer with the one side of diffusion layer, forms or proton exchange membrane two sides formation catalyst layer at the constant humidity laminar surface; The proton exchange membrane two sides is to being called catalyst layer, constant humidity layer, diffusion layer, and hot pressing is self-humidifying proton exchange film fuel cell membrane electrode after taking out, and the constant humidity layer of the self-humidifying membrane electrode of this method preparation can have influence on the diffusion of reacting gas.
Chinese patent ZL200710051269.2 discloses " a kind of through bipolar plates maintenance water balance for proton exchange film fuel cell "; This patent application adopts the two sides of bipolar plates to pass through hydrogen/oxygen respectively; Middle logical cooling water; This bipolar plates contains the gel pore, and possess hydrophilic property; When Proton Exchange Membrane Fuel Cells moves,,, can accomplish the discharge of the humidification and the product water of Proton Exchange Membrane Fuel Cells simultaneously through the pressure of adjustment reacting gas and cooling water by the cooling water in the cooling water runner.This method can not reach requirement steady in a long-term in practical operation.
People such as Qin Qun (Qin Qun; Luo Zhiping; Gui Dan; Deng. battery; 2008,38 (2): 0079-0082) proposed a kind of micro cavity layer structures model, through the carbon dust of forming this microporous layers is carried out acid treatment; Strengthened the hydrophily of carbon dust, made microporous layers (MPL) with hydrophilic/hydrophobic composite pore structural.This microporous layers and the Nafion212 film that scribbles catalyst are assembled into cell carry out the performance test discovery: outside having, under the situation of humidification, do not use the battery of the MPL assembling of preparation not compare with the battery of the traditional MPL of use, performance increases.In current density is 400 mAcm
-2The time, the voltage of battery has improved about 0.1 V, realized to a certain extent battery from humidification.But this method does not also find effective method to be used for measuring the structure and the distribution situation of MPL hydrophilic pores and weep hole at present; And the content of hydrophily carbon dust can not be confirmed accurately among the MPL.
Up to the present, all there is certain defective in the balance method of water among the PEMFC, all can not reaches well from humidification/exempt from humidification effect.
Summary of the invention
For solving defective and the deficiency that existing correlation technique exists, the object of the present invention is to provide a kind of self-humidifying fuel cell composite catalyst, be applied to fuel cell membrane electrode, can improve catalyst activity simultaneously and realize that membrane electrode is from humidification/exempt from moisturization.
The present invention also aims to provide the preparation method of above-mentioned self-humidifying fuel cell composite catalyst.Through use above-mentioned compound from humidification/exempt from humidification catalyst realize membrane electrode from humidification/exempt from humidification, when improving catalyst activity, it is outstanding in humidification/exempt from moisturization that fuel cell is had.
A further object of the present invention is to provide the application of above-mentioned self-humidifying fuel cell composite catalyst.
Self-humidifying fuel cell composite catalyst of the present invention; Be on complex carrier, to support noble metal to be prepared from; Noble metal and complex carrier are even mixed state; On carbon carrier and form, water conservation material, metal oxide and carbon carrier are even mixed state to said complex carrier by water conservation material and metal oxide codeposition; The quality percentage composition of water-retaining property material is 2%～9% in the composite catalyst, and the quality percentage composition of metal oxide is 0.5%～5%, and the quality percentage composition of noble metal is 10%～45%, and surplus is a carbon carrier.
For further realizing the object of the invention, said water conservation material is silicon dioxide, titanium dioxide or tungstic acid.
Said metal oxide is ruthenium-oxide or yttrium oxide.
Said noble metal is platinum, platinum ruthenium or platinum palladium.
Said carbon carrier is XC-72R carbon black or CNT (carbon nano-tube).
The preparation method of self-humidifying fuel cell composite catalyst comprises the steps:
(1) metal precursor is added in the concentrated hydrochloric acid, and with its dissolve lysate, then lysate is joined in the volatile organic solvent, obtain mixed solution; The mass and size concentration of metal precursor is 10g/L～30g/L in the mixed solution;
(2) with the organic precursor of water-retaining property material and volatile organic solvent by volume 1:30～1:50 mix, obtain mixed solution;
(3) the step (1) and step (2) to obtain a mixed solution of 2:1 to 20:1 by volume mixed to obtain a mixture, then the mixture was added to the oxidized carbon support, followed by stirring at room temperature 0.5 h ~ 3h and sonicated 0.5h ~ 1h the metal precursor and a water retention of the organic material precursor on a carbon support mixed, the mixture was evaporated ethanol bath, the remaining solution was placed in 70 ℃ ~ 100 ℃ vacuum drying box 5h ~ 8h vacuum dried to remove the volatile organic solvent, and finally in an inert gas atmosphere at 300 ℃ ~ 600 ℃ treatment 3? h ~ 8h, after cooling the composite carrier; carbon carrier mass and metal precursor and water- The total mass of substance ratio of 50:3 ~ 50:6;
(4) be carrier with the complex carrier for preparing in the step (3), adopt the preparation of high pressure organic sol method to support the composite catalyst of noble metal.
The said metal precursor of step (1) is RuCl
33H
2O or IrCl
3NH
2O; The organic precursor of said water-retaining property material is tetraethoxysilane, tetrabutyl titanate or silico-tungstic acid; Said volatile organic solvent is ethanol or acetone.
High pressure organic sol method concrete steps are:
(1) with after alcohols reducing agent, complexing agent, the mixing of slaine presoma, stirs 10min～60min, get lysate; The volume of alcohols reducing agent is 0.05ml/mg～0.15ml/mg with the volume mass ratio of complexing agent quality, and the mass and size concentration of slaine presoma is 1g/L～20g/L in the said lysate; Said metal precursor is the mixture of chloroplatinic acid, ruthenic chloride or chloroplatinic acid and ruthenic chloride;
(2) in lysate, add said complex carrier, stir 12h～48h, get mixed solution liquid; The mass ratio of said complex carrier and slaine presoma is 1:1～2:1;
(3) mixed solution places 120 ℃～160 ℃ reaction kettle for reaction 3h～8h, obtains mixed liquor;
(4) mixed liquor carries out vacuum filtration again after acidic materials adjusting pH value is 1～4, and the gained filter cake is washed with distilled water to and can not detects chloride ion, filter cake vacuumize more then, and cooling promptly obtains composite catalyst.
Said alcohols reducing agent is ethylene glycol, glycerine or glycerine; Said complexing agent is natrium citricum, sodium oxalate, disodium ethylene diamine tetraacetate or sodium tartrate, and said acidic materials are that mass concentration is 5%～10% salpeter solution or sulfuric acid solution.
Be further to realize the object of the invention, the said mixed solution of step (3) is microwave reaction 1min～60min in the microwave reactor of 200W～600W in microwave power.
With above-mentioned composite catalyst as anode catalyst; With commercial platinum C catalyst or above-mentioned composite catalyst is cathod catalyst; Adopt spraying process that said composite catalyst is sprayed at the both sides of proton exchange membrane, can make from humidification/the exempt from good fuel cell membrane electrode of moisturization according to the conventional electrodes preparation procedure.
Exempt from humidifying technology with existing fuel cell and compare, the present invention has the following advantages:
(1) the present invention adopts the mode of metal oxide and the common modified catalyst supports of water-retaining property material, can obtain from humidification/the exempt from good fuel-cell catalyst of moisturization.Directly adopt this catalyst, prepare membrane electrode, can obtain the good membrane electrode of moisture retention with spraying process; Not simple at the Catalytic Layer non-conductive water-retaining property material that mixes; Need not construct one deck water conservation layer; Need in proton exchange membrane, not add the water-retaining property material yet; Avoided because of the interpolation of electron opaque material in Catalytic Layer; The adding of water conservation material in water conservation layer and the proton exchange membrane and cause the problem that the internal resistance of cell increases, so this approach is exempted from one of humidifying film electrode simply approach efficiently for preparation;
(2) interpolation of metal oxide can effectively improve the performance of catalyst among the present invention; For the anodic oxidation of methyl alcohol and the cathodic reduction of oxygen; Adopt an amount of metal oxide modified carrier to improve the anodic oxidation of 20%(methyl alcohol than the activity of such catalysts that makes without the metal oxide modified carrier as the activity of such catalysts that carrier makes) and the 25%(hydrogen reduction) more than; In hydrogen-empty Proton Exchange Membrane Fuel Cells; When adopting catalyst that the metal oxide modified carrier makes as carrier as anode catalyst; Not only can make electrode possess the moisturization of exempting from; Simultaneously, activity also increases than the activity of such catalysts that makes without the metal oxide modified carrier;
(3) preparation method of the present invention is simple, does not need special instrument and equipment, can realize the large-scale production of catalyst.
Description of drawings
Fig. 1 (a) is low power Electronic Speculum (TEM) figure of embodiment 3 prepared composite catalyst;
Fig. 1 (b) is high power Electronic Speculum (TEM) figure of embodiment 3 prepared composite catalyst;
Fig. 2 is that embodiment 1 to embodiment 4 and contrast are implemented embodiment 1 prepared composite catalyst at 0.5MH
2SO
4+ 0.5MCH
3The cyclic voltammogram of OH solution;
Fig. 3 is that embodiment 3 implements embodiment 1 prepared composite catalyst at 0.5MH with contrast
2SO
4In the hydrogen reduction curve chart;
Fig. 4 is for implementing embodiment 1 prepared composite catalyst with embodiment 3 and contrast respectively and being the membrane electrode that makes of anode catalyst performance chart of long-time discharge under the humidification condition not fully in hydrogen-air-fuel battery with the commercial 40wt%Pt/C catalyst of JM that embodiment 2 is implemented in contrast.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and embodiment.
The specific embodiment of the present invention: water-retaining property material and metal oxide common deposited are processed complex carrier on carbon carrier, on complex carrier, support noble metal again and be prepared into composite catalyst.Use this catalyst as anode catalyst, and use spraying process that this Preparation of Catalyst is become membrane electrode, be assembled into battery then.
Embodiment 1
(1) preparation of complex carrier: the tetraethoxysilane of 2ml is joined in the ethanol, be made into tetraethoxysilane/ethanolic solution of 100ml, obtain mixed solution;
(2) with 1 gram RuCl
33H
2O joins in the ethanol, is made into the RuCl of 20mg/ml
33H
2The O/ ethanolic solution obtains mixed solution;
(3) get the mixed solution (volume ratio is 19.7:1) that the step (2) of mixed solution that 5.9ml step (1) obtains and 0.3ml obtains; Add the XC-72R carbon black of 500mg then through oxidation processes; At room temperature stir and ultrasonic each half an hour; Tetraethoxysilane and metal precursor and carbon black are mixed; 70 ℃ of water-bath evaporation 4h; After evaporating ethanol; Put into 80 ℃ of vacuum drying chambers; Vacuumize 6h and further remove remaining ethanol, then under inert atmosphere in 300 ℃ of sintering 8h, cooling; Promptly make complex carrier; Dioxide-containing silica is 6% in this complex carrier, and ruthenium-oxide content is 0.5%, can be expressed as 6.5wt%RuSiOx/C;
(4) Preparation of catalysts: with the complex carrier for preparing in the step (3) is carrier; Concrete steps are: in the ethylene glycol of 15ml, add the 200mg natrium citricum; The 132mg chloroplatinic acid; After being stirred to natrium citricum and dissolving fully; Complex carrier in lysate after the adding 200mg oxidation processes; After being stirred to complex carrier and evenly distributing, 120 ℃ of reaction kettle for reaction 6 hours obtain mixed liquor; Said mixed liquor is 5% HNO through mass concentration
3After solution adjusting pH value was 3, again through vacuum filtration, the gained filter cake was washed with distilled water to and can not detects chloride ion, filter cake vacuumize more then, and cooling obtains composite catalyst.Wherein ethylene glycol is solvent and reducing agent, and natrium citricum is a complexing agent, and chloroplatinic acid is the presoma of platinum, and in the composite catalyst of preparation, the quality percentage composition of platinum is 20wt%, and the mass ratio of ruthenium-oxide and silica is 1:12.
The methyl alcohol electro catalytic activity is estimated: adopt the German ZAHNER IM6e of company electrochemical workstation, the PINE rotating disk electrode (r.d.e) is estimated the methyl alcohol electro catalytic activity of catalyst.At 0.5MH
2SO
4+ 0.5MCH
3Test in the OH solution, sweep fast 50mV/s, voltage scan range-0.2V ~ 1.0V.5mg step (2) prepared composite catalyst is dispersed in 1ml 0.25wt% polytetrafluoroethylene (Teflon) and perfluor-3; In the copolymer solution (Nafion) of 6-diepoxy-4-methyl-7-decene-sulfuric acid; And get its 5 μ L and be applied to the glass-carbon electrode surface that diameter is 5mm, treat after the infrared oven dry as work electrode; Saturated Ag/AgCl electrode is as reference electrode; Platinum filament is as auxiliary electrode.
Hydrogen reduction performance evaluation: adopt the German ZAHNER IM6e of company electrochemical workstation, the PINE rotating disk electrode (r.d.e) is estimated the methyl alcohol electro catalytic activity of catalyst.At 0.5MH
2SO
4Test in the solution, sweep fast 5mV/s, voltage scan range 0.2V ~ 1.0V, rotating speed are 1600rpm.The 5mg catalyst is dispersed among the 1ml 0.25wt% Nafion, and gets its 5 μ l and be applied to the glass-carbon electrode surface that diameter is 5mm, treats after the infrared oven dry as work electrode; Saturated Ag/AgCl electrode is as reference electrode; Platinum filament is as auxiliary electrode.
Exempt from the preparation of humidifying film electrode: with the composite catalyst of above-mentioned preparation as anode catalyst; With commercial Pt/C catalyst (Johnson Matthey; Hispec4100; 40wt%Pt) as cathod catalyst; Use direct spraying technology (ZL200610035275.4) preparation membrane electrode under the infrared lamp illumination, the platinum carrying capacity of anode and negative electrode is respectively 0.1mg/cm
2With 0.2 mg/cm
2In the slurry of catalyst, the ratio of catalyst and dried Nafion is 2.5:1, and the employing isopropyl alcohol is a solvent.Concrete steps are following: will pass through H
2O
2The proton exchange membrane of handling with sulfuric acid solution is fixed on the frame mold; The mould that fixes proton exchange membrane is placed under the infrared lamp, a certain amount of above-mentioned catalyst pulp is sprayed on the both sides of proton exchange membrane, constitute negative electrode and anode with spray gun.
The test of membrane electrode: the performance to the membrane electrode that makes in Arbin FCTS fuel battery test system is tested; Above membrane electrode is loaded in the small-sized test battery; Earlier under humidified condition, membrane electrode is carried out activation processing; The humidification temperature of hydrogen and air and battery temperature are 50 ℃; Temperature with the dew point humidification of air and hydrogen is reduced to room temperature then; Promptly under the condition of humidification not, the performance of electrode is tested; Battery temperature is 50 ℃, the current density during the record different time under the 0.6V voltage.
Through testing: the methyl alcohol oxidation current of the composite catalyst that present embodiment makes (forward scan peak current) density is 0.45A/mgPt, and the oxygen reduction current density is 0.14A/mgPt.The membrane electrode that makes as anode catalyst is at 0.6V and exempt from fully under the humidification condition, and current density is 580 mA/cm
2, move 10 hours continuously, current density decays to 530mA/cm
2, shown certain from the humidification effect.
6.5wt%RuSiOx/C preparation in the preparation similar embodiment 1 of complex carrier; Different is: get mixed solution 6ml that step among the embodiment 1 (1) obtains, get the mixed solution 1.2ml that step among the embodiment 1 (2) obtains; Get the CNT (carbon nano-tube) of 500mg through oxidation processes; Sintering temperature is 400 ℃; Roasting time 5h, silica content is 6wt% in this carrier, ruthenium-oxide content is 2wt%; Can be expressed as 8wt%RuSiOx/C, the mass ratio of ruthenium-oxide and silica is 1:3; The testing procedure of Preparation of catalysts step, membrane electrode preparation process, methyl alcohol electrocatalysis characteristic evaluation procedure, hydrogen reduction performance evaluation step and membrane electrode is all with embodiment 1.
Through testing: the methyl alcohol oxidation current of the catalyst that present embodiment makes (forward scan peak current) density is 0.59A/mgPt, and the oxygen reduction current density is 0.15A/mgPt.The membrane electrode that makes as anode catalyst is at 0.6V and exempt from fully under the humidification condition, and current density is 630 mA/cm
2, move 10 hours continuously, current density decays to 610mA/cm
2, shown preferably from the humidification effect.
Embodiment 3
6.5wt%RuSiOx/C preparation in the preparation similar embodiment 1 of complex carrier; Different is: get mixed solution 6.1ml that step among the embodiment 1 (1) obtains, get the mixed solution 1.7ml that step among the embodiment 1 (2) obtains; Sintering temperature is 500 ℃; Silica content is 6wt% in this carrier; Ruthenium-oxide content is 3wt%; Can be expressed as 9wt%RuSiOx/C, the mass ratio of ruthenium-oxide and silica is 1:2; The testing procedure of Preparation of catalysts step, membrane electrode preparation process, methyl alcohol electrocatalysis characteristic evaluation procedure, hydrogen reduction performance evaluation step and membrane electrode is all with embodiment 1.
Fig. 1 (a) and Fig. 1 (b) structural characterization figure for adopting JEOL JEM2100 Electronic Speculum that this composite catalyst is carried out, as can be seen from the figure, this composite catalyst is evenly distributed, and granularity is about 2.5nm.
Embodiment 1 is implemented in contrast
The preparation of complex carrier: get the mixed solution that 5.9ml embodiment 1 step (1) obtains, add the XC-72R carbon black of 500mg through oxidation processes, other preparation processes are with embodiment 1, and dioxide-containing silica is 6% in the complex carrier that makes, and can be expressed as 6wt%SiO
2/ C, the testing procedure of Preparation of catalysts step, membrane electrode preparation process, methyl alcohol electrocatalysis characteristic evaluation procedure, hydrogen reduction performance evaluation step and membrane electrode is all with embodiment 1.
Fig. 3 be embodiment 3 with comparative example 1 at 0.5MH
2SO
4Hydrogen reduction comparison diagram in the solution.The result shows: the composite catalyst comparison that embodiment 3 makes through the metal oxide modified carriers has improved 37.5% than the oxygen cathode reducing activity of the composite catalyst that embodiment 1 makes without the metal oxide modified carrier.
The composite catalyst in adopting the commercial 40wt%Pt/C catalyst replaced of JM embodiment 3, the testing procedure of membrane electrode preparation process and membrane electrode is all with embodiment 3.
Fig. 4 is the membrane electrode that makes of anode catalyst performance chart of long-time discharge under the humidification condition not fully in hydrogen-air-fuel battery for implementing embodiment 1 prepared composite with embodiment 3 and contrast respectively from the commercial 40wt%Pt/C catalyst of JM that embodiment 2 is implemented in humidification catalyst and contrast.The result shows: contrast is implemented not possess from humidifying capacity through the catalyst of handling from humidification among the embodiment 2; And contrast is implemented among the embodiment 1 membrane electrode that the catalyst of containing metal oxide not makes with contrast; With the composite catalyst of embodiment 3 preparation is that membrane electrode that anode catalyst prepares shows higher battery performance and better from the humidification effect; At 0.6V; Battery temperature is 50 ℃; Gas pressure is 20psi and exempts from fully under the humidification condition that its current density is 680 mA/cm
2, move 10 hours continuously, the current density 30mA/cm that decayed
2, shown preferably from the humidification effect.
Embodiment 4
The testing procedure of the preparation process of composite catalyst, membrane electrode preparation process, methyl alcohol electrocatalysis characteristic evaluation procedure, hydrogen reduction performance evaluation step and membrane electrode is all with embodiment 1, and different is: complex carrier is at 600 ℃, roasting 3h under the inert atmosphere; The mixed solution that step (1) obtains is got the mixed solution that 6.2ml, step (1) obtain and is got 3ml; Silica content is 6wt% in the prepared composite carrier; Ruthenium-oxide content is 5wt%, can be expressed as 11wt%RuSiOx/C, and the mass ratio of ruthenium-oxide and silica is 5:6; It is that chloroplatinic acid with 59mg is the presoma of platinum that composite catalyst prepares in the process, compound in the humidification catalyst content of Pt be 10wt%.
Fig. 2 is that embodiment 1 to embodiment 4 and comparative example's 1 prepared composite catalyst are at 0.5MH
2SO
4+ 0.5MCH
3The cyclic voltammogram of OH solution.The result shows: the catalyst that process metal oxide modified carrier makes has improved more than 20% than the methanol oxidation activity of the catalyst that makes without the metal oxide modified carrier.
Through testing: the methyl alcohol oxidation current of embodiment 4 prepared composite catalysts (forward scan peak current) density is 0.52A/mgPt, and the hydrogen reduction current density is 1.5A/mgPt.The membrane electrode that makes as anode catalyst is at 0.6V and exempt from fully under the humidification condition, and current density is 600 mA/cm
2, move 10 hours continuously, current density decays to 570mA/cm
2, shown certain from the humidification effect.
Embodiment 5
The 6.5%RuSiOx/C preparation has following difference: get the mixed solution 0.45ml that step among the embodiment 1 (2) obtains, and this mixed solution is the IrCl of 20mg/ml in the preparation similar embodiment 1 of complex carrier
3NH
2The O/ ethanolic solution, silica content is 6wt% in the prepared carrier, yttrium oxide content is 1wt%, can be expressed as 7%IrSiOx/C, and the mass ratio of yttrium oxide and silicon dioxide is 1:6.
The testing procedure of the preparation process of composite catalyst, membrane electrode preparation process, methyl alcohol electrocatalysis characteristic evaluation procedure, hydrogen reduction performance evaluation step and membrane electrode is all with embodiment 1.
Through testing: methyl alcohol oxidation current (forward scan peak current) density of the composite catalyst of present embodiment preparation is 0.48A/mgPt, and the oxygen reduction current density is 0.14A/mgPt; The membrane electrode that makes as anode catalyst is at 0.6V and exempt from fully under the humidification condition, and current density is 600 mA/cm
2, move 10 hours continuously, current density decay 20 ~ 30mA/cm
2
The preparation of complex carrier is similar to 6.5%RuSiOx/C preparation among the embodiment 1; Following difference is arranged: get the mixed solution 7.2ml that embodiment 1 step (1) obtains; And this mixed solution is that the tetrabutyl titanate of 2ml joins in the ethanol, is made into tetrabutyl titanate/ethanolic solution of 100ml.Titanium oxide content is 6wt% in the prepared complex carrier, and ruthenium-oxide content is 3wt%, can be expressed as 9wt%RuTiOx/C, and the mass ratio of ruthenium-oxide and titanium oxide is 1:2..
The testing procedure of the preparation process of composite catalyst, membrane electrode preparation process, methyl alcohol electrocatalysis characteristic evaluation procedure, hydrogen reduction performance evaluation step and membrane electrode is all with embodiment 1.
Through testing: catalyst methyl alcohol oxidation current (forward scan peak current) density of present embodiment preparation is 0.58A/mgPt, and the hydrogen reduction current density is 0.16A/mgPt; The membrane electrode that makes as anode catalyst is at 0.6V and exempt from fully under the humidification condition, and current density is 650 mA/cm
2, move 10 hours continuously, current density decay 30 ~ 40mA/cm
2
Embodiment 7
(1) preparation of complex carrier: with embodiment 1;
(2) Preparation of catalysts: with the complex carrier for preparing in the step (1) is carrier, adopts the high pressure organic sol method to prepare complex carrier and supports the compound from the humidification catalyst of noble metal platinum and ruthenium; Its way is: in the 15ml glycerine, add the 3ml deionized water; The 200mg natrium citricum; 88mg chloroplatinic acid and 44mg ruthenic chloride; After being stirred to the natrium citricum dissolving; Add the 200mg complex carrier; After being stirred to it and evenly distributing, in 160 ℃ of autoclaves, react 8h, then through neutralization, washing, dry and make catalyst.Wherein glycerine is a reducing agent, and natrium citricum is a complexing agent, and chloroplatinic acid and ruthenic chloride are respectively the presoma of platinum and ruthenium, and the ratio of the atomic weight of platinum ruthenium is 1:1, and in the composite catalyst of preparation, the content of platinum ruthenium is 20wt%.
(3) testing procedure of membrane electrode preparation process, methyl alcohol electrocatalysis characteristic evaluation procedure, hydrogen reduction performance evaluation step and membrane electrode is all with embodiment 1.
Through testing: the composite catalyst of present embodiment preparation, methyl alcohol oxidation current (forward scan peak current) density is 0.68A/mgPt, the oxygen reduction current density is 0.17A/mgPt; The membrane electrode that makes as anode catalyst is at 0.6V and exempt from fully under the humidification condition, and current density is 670 mA/cm
2, move 10 hours continuously, current density decay 20mA/cm
2
Embodiment 8
(1) preparation of complex carrier: with embodiment 1;
(2) Preparation of catalysts: with the complex carrier for preparing in the step (1) is carrier; Concrete steps are: in the ethylene glycol of 15ml, add the 287mg natrium citricum; 50.5mg chloroplatinic acid and 52mg palladium bichloride; After being stirred to natrium citricum and dissolving fully; Step (1) prepared composite carrier after the adding 200mg oxidation processes; After being stirred to the even distribution of complex carrier, in the microwave reactor of 400W, reacting 1min, is 5% H then through mass concentration
2SO
4Solution is regulated after pH value is 2, vacuum filtration again, and the gained filter cake is washed with distilled water to and can not detects chloride ion, and filter cake vacuumize is more then cooled off and is promptly obtained composite catalyst.Wherein ethylene glycol is solvent and reducing agent, and natrium citricum is a complexing agent, and chloroplatinic acid and palladium bichloride are respectively the presoma of platinum and palladium, and in the composite catalyst of preparation, the content of platinum palladium is 20wt%.
(3) testing procedure of membrane electrode preparation process, methyl alcohol electrocatalysis characteristic evaluation procedure, hydrogen reduction performance evaluation step and membrane electrode is all with embodiment 1.
Through testing: composite catalyst methyl alcohol oxidation current (forward scan peak current) density of present embodiment preparation is 0.72A/mgPt, and the hydrogen reduction current density is 0.15A/mgPt; The membrane electrode that makes as anode catalyst is at 0.6V and exempt from fully under the humidification condition, and current density is 660 mA/cm
2, move 10 hours continuously, current density decay 20mA/cm
2
Claims (10)
1. self-humidifying fuel cell composite catalyst; It is characterized in that said composite catalyst is on complex carrier, to support noble metal to be prepared from; Noble metal and complex carrier are even mixed state; On carbon carrier and form, water conservation material, metal oxide and carbon carrier are even mixed state to said complex carrier by water conservation material and metal oxide codeposition; The quality percentage composition of water-retaining property material is 2%～9% in the composite catalyst, and the quality percentage composition of metal oxide is 0.5%～5%, and the quality percentage composition of noble metal is 10%～45%, and surplus is a carbon carrier.
2. self-humidifying fuel cell composite catalyst according to claim 1 is characterized in that said water conservation material is silicon dioxide, titanium dioxide or tungstic acid; Said metal oxide is ruthenium-oxide or yttrium oxide; Said noble metal is platinum, platinum ruthenium or platinum palladium; Said carbon carrier is XC-72R carbon black or CNT (carbon nano-tube).
3. the preparation method of claim 1 or 2 said self-humidifying fuel cell composite catalysts is characterized in that comprising the steps:
(1) metal precursor is added in the concentrated hydrochloric acid, and with its dissolve lysate, then lysate is joined in the volatile organic solvent, obtain mixed solution; The mass and size concentration of metal precursor is 10g/L～30g/L in the mixed solution;
(2) with the organic precursor of water-retaining property material and volatile organic solvent by volume 1:30～1:50 mix, obtain mixed solution;
(3) the step (1) and step (2) to obtain a mixed solution of 2:1 to 20:1 by volume mixed to obtain a mixture, then the mixture was added to the oxidized carbon support, followed by stirring at room temperature 0.5 h ~ 3h and sonicated 0.5h ~ 1h the metal precursor and a water retention of the organic material precursor on a carbon support mixed, the mixture was evaporated ethanol bath, the remaining solution was placed in 70 ℃ ~ 100 ℃ vacuum drying box 5h ~ 8h vacuum dried to remove the volatile organic solvent, and finally in an inert gas atmosphere at 300 ℃ ~ 600 ℃ treatment 3? h ~ 8h, after cooling the composite carrier; carbon carrier mass and metal precursor and water-the total mass of substance ratio of 50:3 ~ 50:6;
(4) be carrier with the complex carrier for preparing in the step (3), adopt the preparation of high pressure organic sol method to support the composite catalyst of noble metal.
4. preparation method according to claim 3 is characterized in that said metal precursor is RuCl
33H
2O or IrCl
3NH
2O; The organic precursor of said water-retaining property material is tetraethoxysilane, tetrabutyl titanate or silico-tungstic acid; Said volatile organic solvent is ethanol or acetone.
5. according to claim 3 or 4 described preparation methods, it is characterized in that said high pressure organic sol method concrete steps are:
(1) with after alcohols reducing agent, complexing agent, the mixing of slaine presoma, stirs 10min～60min, get lysate; The volume of alcohols reducing agent is 0.05ml/mg～0.15ml/mg with the volume mass ratio of complexing agent quality, and the mass and size concentration of slaine presoma is 1g/L～20g/L in the said lysate; Said metal precursor is the mixture of chloroplatinic acid, ruthenic chloride or chloroplatinic acid and ruthenic chloride;
(2) in lysate, add said complex carrier, stir 12h～48h, get mixed solution; The mass ratio of said complex carrier and slaine presoma is 1:1～2:1;
(3) mixed solution obtains mixed liquor in 120 ℃～160 ℃ reaction kettle for reaction 3h～8h;
(4) mixed liquor carries out vacuum filtration again after acidic materials adjusting pH value is 1～4, and the gained filter cake is washed with distilled water to and can not detects chloride ion, filter cake vacuumize more then, and cooling promptly obtains composite catalyst.
6. preparation method according to claim 5 is characterized in that said alcohols reducing agent is ethylene glycol, glycerine or glycerine.
7. preparation method according to claim 5 is characterized in that said complexing agent is natrium citricum, sodium oxalate, disodium ethylene diamine tetraacetate or sodium tartrate.
8. preparation method according to claim 5 is characterized in that said acidic materials are that mass concentration is 5%～10% salpeter solution or sulfuric acid solution.
9. preparation method according to claim 5 is characterized in that the said mixed solution of step (3) is microwave reaction 1min～60min in the microwave reactor of 200W～600W in microwave power.
10. claim 1 or 2 application of said self-humidifying fuel cell composite catalyst in fuel cell membrane electrode; Said fuel cell membrane electrode comprises anode, negative electrode and the proton exchange membrane between anode and negative electrode, it is characterized in that: the both sides that said composite catalyst are sprayed at proton exchange membrane; As anode catalyst, is cathod catalyst with commercial platinum C catalyst catalyst or said composite catalyst with above-mentioned composite catalyst.
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