CN103084167A - Preparation method of proton exchange membrane fuel cell catalyst - Google Patents
Preparation method of proton exchange membrane fuel cell catalyst Download PDFInfo
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Abstract
The invention provides a preparation method of a proton exchange membrane fuel cell catalyst. The preparation method comprises the following steps of: mixing a noble metal halide solution and carbon black, adjusting the pH value to 2.5-10.5, and then carrying out ultrasonic wave stirring to obtain precursor liquid, wherein the noble metal halide solution is platinum halide or a mixture of platinum halide and ruthenium halide; adding the precursor liquid to a sodium borohydride solution, and carrying out ultrasonic wave stirring to obtain a mixed liquid; and standing, filtering, washing and drying the mixed liquid to obtain the proton exchange membrane fuel cell catalyst. The proton exchange membrane fuel cell catalyst prepared by the method has uniform particle size and high electrochemical performance.
Description
Technical field
The present invention relates to catalyst field, relate in particular to a kind of preparation method of catalyst of fuel batter with proton exchange film.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind ofly novel chemical energy can be directly changed into the device of electric energy.Because the interior of pem cell no-rotary part can consume, without burning, energy conversion efficiency is not limited by Carnot cycle, so it has higher energy conversion efficiency.And pem cell adopts clean energy resource, and as hydrogen and methyl alcohol etc., without oxysulfide and emitting nitride, without harm, the feature of environmental protection is high to environment.Pem cell also has the condition of work gentleness, and volume is little, and is lightweight, and the characteristics of safety durable are widely used as portable power source, itself or desirable electrical source of power.
At present, more and more be subject to the attention of various countries for the development of Proton Exchange Membrane Fuel Cells.Proton Exchange Membrane Fuel Cells comprises two electrodes and the PEM between two electrodes, and electrode comprises supporting layer and is overlying on the eelctro-catalyst of support layer surface.Existing catalyst of fuel batter with proton exchange film is mainly platinum or platinum-ruthenium alloys.The effect of eelctro-catalyst is hydrogen catalyzed (or hydrogeneous reformed gas) and oxygen generation electrochemical reaction, eelctro-catalyst has material impact to the battery activity.
Performance and its preparation method of eelctro-catalyst are closely related, and prior art provides the preparation method of multiple catalysts, and comparatively commonly used is following several:
Infusion process, it is the most popular method [J.B.Goodenough, A.Hamnett, B.J.Kemmedy, ETC.Electrochimica Acta, Vol15, No.1pp.199-207,1990] of preparation carrier metal catalyst.Its basic operation process is: the solution of carrier being put into slaine fully floods, and then adds reducing agent reducing metal ion.
Metallic vapour method [Wu Shihua, willow army, Wang Xukun etc., petrochemical industry, 18(6), 361,1989], it is first with the metal vaporization, then metal is agglomerated on carrier surface, can prepare metal dispersity so higher, active better catalyst.
Metal ion match oxidation-reduction method [Masahiro Watanabe, Makoto Uchida, Satoshi Motoo, J.Electroanal.Chem.229 (1987) 395-406], the method is that metal ion and reduction-state coordination ion are formed complex, then add oxidant, oxidation part and metal ion form metastable solution.Under certain condition, add carrier, metal deposits on carrier, forms catalyst particles.
Nano metal bunch synthetic method, the method are a kind of brand-new method [Schmidt, M.Noeske, H.A.Gasteiger, R.J.Behm, J.Electrochem.Soc., Vol.145, No.3, March1998], in suitable organic phase, metal ion and reducing agent reaction, under the stabilizing agent existence condition, generate nano metal bunch.
Template [Jung, Y.S.; Lee, J.H.; Lee, J.Y.; Ross, C.A.Nano.Lett.2010,10,3722-3726] and surfactant method [Sakamoto, Y.; Fukuoka, A.; Higuchi, T.; Shimomura, N.; Inagaki, S.; Ichikawa, M.J.Phys.Chem.B2004,108,853-858], above-mentioned two kinds of methods can be used for synthesizing the catalyst with certain geometric properties.
It is generally acknowledged that the platinum particulate should be non-crystal state in 4 nanometer range, the electro-chemical activity best [Masahiro Watanabe, Makoto Uchida, Satoshi Motoo, J.Electroanal.Chem.229 (1987) 395-406] of catalyst performance.But said method all is difficult to the uniform catalyst of preparation microstate, and gathering, the catalyst grain size uniformity that its catalyst that obtains generally can produce metallic descend, and cause chemical property lower.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method of catalyst of fuel batter with proton exchange film, the catalyst of fuel batter with proton exchange film epigranular that the method makes, and chemical property is high.
The invention provides a kind of preparation method of catalyst of fuel batter with proton exchange film, comprise the following steps:
A) noble metal halide solution and carbon black are mixed, carry out ultrasonic wave behind adjust pH to 2.5 ~ 10.5 and stir, obtain precursor liquid;
Described noble metal halide is platinum halide or platinum halide and the halid mixture of ruthenium;
B) described precursor liquid is added in sodium borohydride solution, carry out obtaining mixed liquor after ultrasonic wave stirs;
C) described mixed liquor is standing, filter, washing and dry, obtain catalyst of fuel batter with proton exchange film.
Preferably, described platinum halide is one or more in chloroplatinic acid, platinic sodium chloride, potassium chloroplatinate, bromoplatinic acid and iodine platinic acid; Described ruthenium halide is one or more in ruthenium trichloride, ruthenium hydrochloride sodium, ruthenium hydrochloride potassium, bromine ruthenic acid and iodine ruthenic acid.
Preferably, the concentration of the middle precious metal ion of described noble metal halide solution is 0.5g/L ~ 10g/L.
Preferably, described steps A) in, adopt ammoniacal liquor adjust pH to 2.5 ~ 10.5.
Preferably, the mass ratio of carbon black and described noble metal halide steps A) is 100:(20 ~ 75).
Preferably, the concentration of described sodium borohydride is 10g/L ~ 100g/L.
Preferably, the mol ratio of described sodium borohydride and noble metal halide is (2 ~ 10): 1.
Preferably, the volume ratio of described sodium borohydride and noble metal halide solution is (0.0007 ~ 0.8): 1.
Preferably, ultrasonic wave mixing time described step B) is 0.5 ~ 1h.
Preferably, ultrasonic wave mixing time described steps A) is 0.5 ~ 1h.
Compared with prior art, the present invention mixes noble metal halide solution and carbon black, carries out ultrasonic wave behind adjust pH to 2.5 ~ 10.5 and stirs, and obtains precursor liquid; Described precursor liquid is added in sodium borohydride solution, carry out obtaining mixed liquor after ultrasonic wave stirs; Described mixed liquor is standing, filter, washing and dry, obtain catalyst of fuel batter with proton exchange film; Described noble metal halide is platinum halide or platinum halide and the halid mixture of ruthenium;
The present invention has changed the mode that adds of borane reducing agent sodium hydride solution, be about to precursor liquid and add in sodium borohydride solution, be aided with ultrasonic wave and stir, can generate at short notice a large amount of noble metal nucleus, control the formation speed of noble metal nucleus, reduced the probability of noble metal nuclei growth; Simultaneously by regulating the pH value of metal halide solution, make noble metal halide generate sediment, the sediment that generates is adsorbed on before being reduced on the carrier carbon black, the noble metal nano particles that can effectively reduce generation in reduction process collides in solution, assembles, grows up, thereby can effectively control the catalyst of fuel batter with proton exchange film particle diameter, finally form at carrier surface the nano particle comparatively uniformly that distributes, and agglomeration can not occur, the catalyst of fuel batter with proton exchange film epigranular that obtains, chemical property is high.
Experimental result shows, the average grain diameter of catalyst of fuel batter with proton exchange film provided by the present invention is 2 ~ 4nm approximately, chemical property is compared with the catalyst of fuel batter with proton exchange film of prior art, and battery peak power density has improved 20% ~ 29%, and peak current density has improved 15% ~ 31%.
Description of drawings
The transmission electron microscope photo of the catalyst of fuel batter with proton exchange film that Fig. 1 provides for the embodiment of the present invention 1;
The particle diameter distribution map of the catalyst of fuel batter with proton exchange film that Fig. 2 provides for the embodiment of the present invention 1;
Fig. 3 is the hydrogen/oxygen fuel cell of the embodiment of the present invention 1 preparation and the polarization curve of hydrogen/oxygen fuel cell that Comparative Examples 1 prepares;
Fig. 4 is the three-electrode system of the embodiment of the present invention 2 preparations and the cyclic voltammetry curve of three-electrode system in methanol solution of Comparative Examples 2 preparations;
Fig. 5 is the methyl alcohol/oxygen fuel cell of the embodiment of the present invention 3 preparations and the polarization curve of methyl alcohol/oxygen fuel cell that Comparative Examples 3 prepares.
The specific embodiment
The invention provides a kind of preparation method of catalyst of fuel batter with proton exchange film, comprise the following steps:
A) noble metal halide solution and carbon black are mixed, carry out ultrasonic wave behind adjust pH to 2.5 ~ 10.5 and stir, obtain precursor liquid;
Described noble metal halide is platinum halide or platinum halide and the halid mixture of ruthenium;
B) described precursor liquid is added in sodium borohydride solution, carry out obtaining mixed liquor after ultrasonic wave stirs;
C) described mixed liquor is standing, filter, washing and dry, obtain catalyst of fuel batter with proton exchange film.
At first the present invention adds carbon black to mix in noble metal halide solution, and regulator solution pH value is also carried out ultrasonic wave and stirred, and obtains precursor liquid.Described noble metal halide is platinum halide or platinum halide and the halid mixture of ruthenium, and wherein, described platinum halide is one or more in chloroplatinic acid, platinic sodium chloride, potassium chloroplatinate, bromoplatinic acid and iodine platinic acid; Described ruthenium halide is one or more in ruthenium trichloride, ruthenium hydrochloride sodium, ruthenium hydrochloride potassium, bromine ruthenic acid and iodine ruthenic acid.The present invention there is no particular restriction for the source of described noble metal halide, can be for generally commercially available.Described noble metal halide is mixed with solution, the size of described solution concentration can affect the effective absorption of noble metal halide solution on carrier, and finally affect the pay(useful) load of noble metal granule on carrier and evenly distribute, if excessive concentration, catalyst granules is easily assembled; If concentration is too low, will cause partially catalyzed agent particle not to be adsorbed onto on carrier.The concentration of the present invention's compositions different from catalyst of fuel batter with proton exchange film and ratio-dependent noble metal halide solution.The concentration of the middle precious metal ion of described noble metal halide solution is preferably 0.5g/L ~ 10g/L, more preferably 1g/L ~ 10g/L.The solvent that dissolves described noble metal halide is preferably the hydrochloric acid solution of deionized water or 0.1 ~ 1mol/L, the more preferably hydrochloric acid solution of deionized water or 0.4 ~ 0.6mol/L.
Add carbon black to mix in the solution of described noble metal halide, the carrier carbon black adsorbs noble metal halide, described carbon black addition is as the criterion with the carrying capacity of carbon black to noble metal halide, after described carbon black is carbon black the absorption of noble metal halide is reached balance the carrying capacity of noble metal halide, the quality of the carbon black absorption noble metal halide of unit mass.In the present invention, the mass ratio of described carbon black and described noble metal halide is 100:(20 ~ 75), be preferably 100:(30 ~ 70), 100:(40 ~ 60 more preferably).The temperature that described carbon black adsorbs noble metal halide is preferably 23 ~ 60 ℃, more preferably 30 ~ 50 ℃; Described carbon black is preferably 0.5 ~ 2h to the time that noble metal halide adsorbs, more preferably 1 ~ 1.5h.
In the present invention, noble metal halide solution and carbon black mix, and regulate pH value to 2.5 ~ 10.5, preferably adopt ammoniacal liquor adjust pH to 2.5 ~ 10.5.When described noble metal halide was platinum halide, the pH value of having adsorbed the noble metal halide solution of carbon black was preferably 2.5 ~ 10.5, and more preferably 3.0 ~ 10.0; When described noble metal halide is platinum halide and the halid mixture of ruthenium, owing to there being ruthenium ion to exist in solution, the halid mixture of platinum halide and ruthenium reduction effect in alkaline environment is better, the pH value of having adsorbed the noble metal halide solution of carbon black is preferably 2.5 ~ 10.5, more preferably 7.0 ~ 10.0, most preferably be 7.5 ~ 9.5.After regulating the pH value, carry out ultrasonic wave and stir, obtain precursor liquid, adopt ultrasonic wave to stir and guaranteed that noble metal halide fully precipitates, evenly is adsorbed onto on carbon black, described ultrasonic wave mixing time is preferably 0.5 ~ 1h, more preferably 0.6 ~ 0.8h.Described ultrasonic wave stirs and preferably carries out at the temperature of 22 ~ 55 ℃, and preferred temperature is 25 ~ 45 ℃.
The present invention is by regulating the pH value of noble metal halide solution, make noble metal halide generate sediment, the sediment that generates is adsorbed on before being reduced on the carrier carbon black, the noble metal nano particles that can effectively reduce generation in reduction process collides in solution, assembles, grows up, thereby the particle diameter of the catalyst of fuel batter with proton exchange film that can effectively control, finally form at carrier surface the nano particle of catalyst of fuel batter with proton exchange film comparatively uniformly that distributes, and agglomeration can not occur.
The present invention adds described precursor liquid in sodium borohydride solution and carries out ultrasonic wave and stir, and obtains mixed liquor.In the present invention, the described precursor liquid mode in sodium borohydride solution of adding is preferably and pours into.Described sodium borohydride is reducing agent, and its reducing power is strong, reduction rate is fast, in the present invention, described sodium borohydride is mixed with the aqueous solution, and the concentration of described sodium borohydride solution is preferably 10g/L ~ 100g/L, more preferably 20g/L ~ 150g/L.In described sodium borohydride and described precursor liquid, the mol ratio of noble metal halide is preferably (2 ~ 10): 1, more preferably (3 ~ 8): 1.The volume ratio of described sodium borohydride and noble metal halide solution is (0.0007 ~ 0.8): 1, be preferably (0.001 ~ 1): and 1, more preferably (0.005 ~ 0.5): 1.Carry out ultrasonic wave when adding described precursor liquid in sodium borohydride solution and stir, the time that described ultrasonic wave stirs is preferably 0.5 ~ 1h, more preferably 0.6 ~ 0.8h.Described ultrasonic wave stirs and preferably carries out at the temperature of 22 ~ 28 ℃, and preferred temperature is 24 ~ 26 ℃.
Add described precursor liquid in sodium borohydride solution and carry out ultrasonic wave and stir the mixed liquor obtain and carry out successively standing, filtration, washing, drying, obtaining catalyst of fuel batter with proton exchange film.The described standing time is preferably 1 ~ 3h, more preferably 1.5 ~ 2.5h.The present invention does not have particular restriction for the mode of described filtration, can be filter type well known to those skilled in the art.Remove filtrate after described mixed liquor is filtered, obtain solid matter, described solid matter is washed, until in the cleaning solution after washing without Cl
-Till, wash described solid matter washing agent used and be preferably deionized water.The solid matter of washes clean is carried out drying, can obtain catalyst of fuel batter with proton exchange film, the present invention does not have particular restriction to the drying mode of described solid matter, can be drying mode well known to those skilled in the art, in the present invention, preferred employing vacuum drying, described vacuum drying temperature is preferably 60 ~ 70 ℃, more preferably 62 ~ 65 ℃.
The catalyst of fuel batter with proton exchange film that makes is sprayed on electrode, is assembled into fuel cell.To the fuel cell test that polarizes, result shows, the fuel cell that the present invention makes is compared with the fuel cell of prior art, and battery peak power density has improved 20% ~ 29%.
The catalyst of fuel batter with proton exchange film that makes is coated on makes membrane electrode on glass-carbon electrode, make three-electrode system with Ag/AgCl electrode and Pt sheet again, described three-electrode system is carried out cyclic voltammetry, result shows, the three-electrode system that the present invention makes is compared with the three-electrode system that prior art makes, and peak current density has improved 15% ~ 31%.
The present invention has changed the mode that adds of borane reducing agent sodium hydride solution, be about to precursor liquid and add in sodium borohydride solution, be aided with ultrasonic wave and stir, can generate at short notice a large amount of noble metal nucleus, control the formation speed of noble metal nucleus, reduced the probability of noble metal nuclei growth; Simultaneously by regulating the pH value of metal halide solution, make noble metal halide generate sediment, the sediment that generates is adsorbed on before being reduced on the carrier carbon black, the noble metal nano particles that can effectively reduce generation in reduction process collides in solution, assembles, grows up, thereby can effectively control the catalyst of fuel batter with proton exchange film particle diameter, finally form at carrier surface the nano particle comparatively uniformly that distributes, and agglomeration can not occur, the catalyst of fuel batter with proton exchange film epigranular that obtains, average grain diameter is 2 ~ 4nm approximately, and chemical property is high.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of catalyst of fuel batter with proton exchange film provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
Chloroplatinic acid is dissolved in the aqueous solution that is mixed with 1L in deionized water, wherein in solution, platinum ion content is 5g/L, add carbon black to adsorb in platinum acid chloride solution, the carrying capacity that makes chloroplatinic acid on carbon black is 20wt%, and ultrasonic wave stirs, obtain suspension, heat described suspension to 50 ℃, kept 1 hour, regulate the pH value to 7.5 of suspension with ammonia spirit, suspension was stirred 30 minutes under Ultrasonic Conditions, obtain precursor liquid.
Get the 1g sodium borohydride, add in the 10mL deionized water, be mixed with sodium borohydride solution.
Described precursor liquid is poured into rapidly in sodium borohydride solution, carried out simultaneously ultrasonic agitation, kept 1 hour, get mixed liquor.
With standing 1 hour of mixed liquor, filter, obtain solid matter, adopt deionized water that described solid matter is washed, until in the cleaning solution after washing without Cl
-Till, the solid matter after washing 60 ℃ of lower vacuum drying, is obtained catalyst of fuel batter with proton exchange film.
Be scattered in absolute ethyl alcohol described catalyst of fuel batter with proton exchange film is ultrasonic, obtain suspension; With described suspension be applied to dry on copper mesh after, carry out transmission electron microscope scanning, the results are shown in Figure 1, the transmission electron microscope photo of the catalyst of fuel batter with proton exchange film that Fig. 1 provides for the embodiment of the present invention 1, as shown in Figure 1, the average grain diameter of the prepared catalyst of fuel batter with proton exchange film of the present invention is 2.8nm.
The particle diameter of measuring described catalyst of fuel batter with proton exchange film distributes, the results are shown in Figure 2, the particle diameter distribution map of the catalyst of fuel batter with proton exchange film that Fig. 2 provides for the embodiment of the present invention 1, as shown in Figure 2, the catalyst of fuel batter with proton exchange film epigranular that the present invention is prepared, particle diameter concentrates on 2 ~ 4nm.
The catalyst of fuel batter with proton exchange film that embodiment 1 is prepared is assembled into hydrogen/oxygen fuel cell, the TGPH-060 carbon paper of 20% waterproof that electrode employing Toray company produces, the spraying catalyst, described catalyst of fuel batter with proton exchange film carrying capacity (take Pt) is 2mg/cm
2, with electrode be placed on model that E.I.Du Pont Company produces be the both sides of PEM of Nafion117 under 130 ℃, 5atm pressure, hot pressing 90s, electrode effective area 9cm
2
To the test that polarizes of described hydrogen/oxygen fuel cell, test condition is that the hydrogen stoichiometric proportion is 1.5, and the oxygen stoichiometric proportion is 2.5, and back pressure is 0, and probe temperature is 25 ℃.Experimental result is referring to Fig. 3, and Fig. 3 is the hydrogen/oxygen fuel cell of the embodiment of the present invention 1 preparation and the polarization curve of hydrogen/oxygen fuel cell that Comparative Examples 1 prepares.Wherein, in Fig. 3,1 and 3 is the polarization curve of the hydrogen/oxygen fuel cell of the embodiment of the present invention 1 preparation.
Comparative Examples 1
The catalyst of fuel batter with proton exchange film that Johnson Matthey company is produced is assembled into hydrogen/oxygen fuel cell, the TGPH-060 carbon paper of 20% waterproof that electrode employing Toray company produces, the spraying catalyst, described catalyst of fuel batter with proton exchange film carrying capacity (take Pt) is 2mg/cm
2, with electrode be placed on model that E.I.Du Pont Company produces be the both sides of PEM of Nafion117 under 130 ℃, 5atm pressure, hot pressing 90s, electrode effective area 9cm
2
To the test that polarizes of described hydrogen/oxygen fuel cell, test condition is that the hydrogen stoichiometric proportion is 1.5, and the oxygen stoichiometric proportion is 2.5, and back pressure is 0, and probe temperature is 25 ℃.Experimental result is referring to Fig. 3, and Fig. 3 is the hydrogen/oxygen fuel cell of the embodiment of the present invention 1 preparation and the polarization curve of hydrogen/oxygen fuel cell that Comparative Examples 1 prepares.Wherein, in Fig. 3,2 and 4 is the polarization curve of the hydrogen/oxygen fuel cell of Comparative Examples 1 preparation.
Result shows, the prepared catalyst of fuel batter with proton exchange film of the present invention is compared with using the catalyst of fuel batter with proton exchange film that Johnson Matthey company produces, and battery peak power density improves 20%.
Chloroplatinic acid/ruthenium hydrochloride is dissolved in the aqueous solution that is mixed with 1L in deionized water, wherein in solution, the content of platinum ion and ruthenium ion is 5g/L, the mol ratio of platinum and ruthenium is 1:0.5, add carbon black to adsorb in chloroplatinic acid/ruthenium hydrochloride solution, the carrying capacity that makes chloroplatinic acid/ruthenium hydrochloride on carbon black is 60wt%, ultrasonic wave stirs, obtain suspension, heat described suspension to 50 ℃, kept 1 hour, regulate the pH value to 7.5 of suspension with ammonia spirit, suspension was stirred 30 minutes under Ultrasonic Conditions, obtain precursor liquid.
Get the 5g sodium borohydride, add in the 10mL deionized water, be mixed with sodium borohydride solution.
Described precursor liquid is poured into rapidly in sodium borohydride solution, carried out simultaneously ultrasonic agitation, kept 1 hour, get mixed liquor.
With standing 1 hour of mixed liquor, filter, obtain solid matter, adopt deionized water that described solid matter is washed, until in the cleaning solution after washing without Cl
-Till, the solid matter after washing 70 ℃ of lower vacuum drying, is obtained catalyst of fuel batter with proton exchange film.
Produce to 50 μ L Aldrich companies, mass concentration is to add the above-mentioned catalyst of fuel batter with proton exchange film of 5mg in 5% Nafion solution, ultrasonic wave disperses 30min, obtains mixed solution; Get the 10 described mixed solutions of μ L and drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode.
With the said film electrode, with the Ag/AgCl electrode as reference electrode, Pt sheet as the three-electrode system that electrode is formed, carry out cyclic voltammetry in the methanol solution through the sulfuric acid of the 0.5mol/L of nitrogen deoxygenation and 0.5mol/L, sweep speed is 20mV/s, experimental result is seen Fig. 4, and Fig. 4 is the three-electrode system of the embodiment of the present invention 2 preparations and the cyclic voltammetry curve of three-electrode system in methanol solution of Comparative Examples 2 preparations.Wherein, in Fig. 4,1 is the cyclic voltammetry curve of three-electrode system in methanol solution of the embodiment of the present invention 2 preparations.
Comparative Examples 2
Produce to 50 μ LAldrich companies, mass concentration is the catalyst of fuel batter with proton exchange film that adds 5mg Johnson Matthey company to produce in 5% Nafion solution, ultrasonic wave disperses 30min, obtains mixed solution; Get the 10 described mixed solutions of μ L and drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode.
With the said film electrode, with the Ag/AgCl electrode as reference electrode, Pt sheet as the three-electrode system that electrode is formed, carry out cyclic voltammetry in the methanol solution through the sulfuric acid of the 0.5mol/L of nitrogen deoxygenation and 0.5mol/L, sweep speed is 20mV/s, experimental result is seen Fig. 4, and Fig. 4 is the three-electrode system of the embodiment of the present invention 2 preparations and the cyclic voltammetry curve of three-electrode system in methanol solution of Comparative Examples 2 preparations.Wherein, in Fig. 4,2 is the cyclic voltammetry curve of three-electrode system in methanol solution of Comparative Examples 2 preparations.
Result shows, the prepared catalyst of fuel batter with proton exchange film of the present invention is compared with using the catalyst of fuel batter with proton exchange film that Johnson Matthey company produces, the negative 40mV that moves of the spike potential of methanol oxidation, and peak current density increases by 25%.
Chloroplatinic acid/ruthenium hydrochloride is dissolved in the aqueous solution that is mixed with 1L in deionized water, wherein in solution, the content of platinum ion and ruthenium ion is 0.5g/L, the mol ratio of platinum and ruthenium is 1:1, add carbon black to adsorb in chloroplatinic acid/ruthenium hydrochloride solution, the carrying capacity that makes chloroplatinic acid/ruthenium hydrochloride on carbon black is 60wt%, ultrasonic wave stirs, obtain suspension, heat described suspension to 50 ℃, kept 1 hour, regulate the pH value to 2.5 of suspension with ammonia spirit, suspension was stirred 30 minutes under Ultrasonic Conditions, obtain precursor liquid.
Get the 5g sodium borohydride, add in the 10mL deionized water, be mixed with sodium borohydride solution.
Described precursor liquid is poured into rapidly in sodium borohydride solution, carried out simultaneously ultrasonic agitation, kept 1 hour, get mixed liquor.
With standing 1 hour of mixed liquor, filter, obtain solid matter, adopt deionized water that described solid matter is washed, until in the cleaning solution after washing without Cl
-Till, the solid matter after washing 80 ℃ of lower vacuum drying, is obtained catalyst of fuel batter with proton exchange film.
The catalyst of fuel batter with proton exchange film that embodiment 3 is prepared is assembled into methyl alcohol/oxygen fuel cell, the TGPH-060 carbon paper spraying catalyst of 20% waterproof that electrode employing Toray company produces, anode is PtRu/C, negative electrode is Pt/C, and described catalyst of fuel batter with proton exchange film carrying capacity (take Pt) is 2mg/cm
2, with electrode be placed on model that E.I.Du Pont Company produces be the both sides of PEM of Nafion117 under 130 ℃, 5atm pressure, hot pressing 90s, electrode effective area 9cm
2
To the test that polarizes of described hydrogen/oxygen fuel cell, test condition is that anode passes into the 0.5mol/L methanol solution, and flow velocity is 1mL/min, and negative electrode is O
2, flow velocity is 250mL/min, and the outlet back pressure is 0atm, and temperature is 25 ℃.Experimental result is seen Fig. 5, and Fig. 5 is the methyl alcohol/oxygen fuel cell of the embodiment of the present invention 3 preparations and the polarization curve of methyl alcohol/oxygen fuel cell that Comparative Examples 3 prepares.Wherein, in Fig. 5,1 and 3 is the polarization curve of the methyl alcohol/oxygen fuel cell of the embodiment of the present invention 3 preparations.
Comparative Examples 3
The catalyst of fuel batter with proton exchange film that Johnson Matthey company is produced is assembled into methyl alcohol/oxygen fuel cell, the TGPH-060 carbon paper spraying catalyst of 20% waterproof that electrode employing Toray company produces, anode is PtRu/C, negative electrode is Pt/C, and described catalyst of fuel batter with proton exchange film carrying capacity (take Pt) is 2mg/cm
2, with electrode be placed on model that E.I.Du Pont Company produces be the both sides of PEM of Nafion117 under 130 ℃, 5atm pressure, hot pressing 90s, electrode effective area 9cm
2
To the test that polarizes of described methyl alcohol/oxygen fuel cell, test condition is that anode passes into the 0.5mol/L methanol solution, and flow velocity 1mL/min, negative electrode are O
2, flow velocity is 250mL/min, and the outlet back pressure is 0atm, and temperature is 25 ℃.Experimental result is seen Fig. 5, and Fig. 5 is the methyl alcohol/oxygen fuel cell of the embodiment of the present invention 3 preparations and the polarization curve of methyl alcohol/oxygen fuel cell that Comparative Examples 3 prepares.Wherein, in Fig. 5,2 is the polarization curve of the methyl alcohol/oxygen fuel cell of Comparative Examples 3 preparations.
Result shows, compare with the methyl alcohol/oxygen fuel cell of the catalyst of fuel batter with proton exchange film preparation of adopting Johnson Matthey company to produce, the methyl alcohol of the prepared catalyst of fuel batter with proton exchange film preparation of the present invention/oxygen fuel cell peak power density improves 29%.
Chloroplatinic acid/ruthenium hydrochloride is dissolved in the aqueous solution that is mixed with 1L in deionized water, wherein in solution, the content of platinum ion and ruthenium ion is 10g/L, the mol ratio of platinum and ruthenium is 1:1, add carbon black to adsorb in chloroplatinic acid/ruthenium hydrochloride solution, the carrying capacity that makes chloroplatinic acid/ruthenium hydrochloride on carbon black is 30wt%, ultrasonic wave stirs, obtain suspension, heat described suspension to 50 ℃, kept 1 hour, regulate the pH value to 5 of suspension with ammonia spirit, suspension was stirred 30 minutes under Ultrasonic Conditions, obtain precursor liquid.
Get the 5g sodium borohydride, add in the 10mL deionized water, be mixed with sodium borohydride solution.
Described precursor liquid is poured into rapidly in sodium borohydride solution, carried out simultaneously ultrasonic agitation, kept 1 hour, get mixed liquor.
With standing 1 hour of mixed liquor, filter, obtain solid matter, adopt deionized water that described solid matter is washed, until in the cleaning solution after washing without Cl
-Till, the solid matter after washing 80 ℃ of lower vacuum drying, is obtained catalyst of fuel batter with proton exchange film.
Produce to 50 μ L Aldrich companies, mass concentration is to add the above-mentioned catalyst of fuel batter with proton exchange film of 5mg in 5% Nafion solution, ultrasonic wave disperses 30min, obtains mixed solution; Get the 10 described mixed solutions of μ L and drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode.
With the said film electrode, with the Ag/AgCl electrode as reference electrode, Pt sheet as the three-electrode system that electrode is formed, carry out cyclic voltammetry in the methanol solution through the sulfuric acid of the 0.5mol/L of nitrogen deoxygenation and 0.5mol/L, sweep speed is 20mV/s.
Comparative Examples 4
Produce to 50 μ LAldrich companies, mass concentration is the catalyst of fuel batter with proton exchange film that adds 5mg Johnson Matthey company to produce in 5% Nafion solution, ultrasonic wave disperses 30min, obtains mixed solution; Get the 10 described mixed solutions of μ L and drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode.
With the said film electrode, with the Ag/AgCl electrode as reference electrode, Pt sheet as the three-electrode system that electrode is formed, carry out cyclic voltammetry in the methanol solution through the sulfuric acid of the 0.5mol/L of nitrogen deoxygenation and 0.5mol/L, sweep speed is 20mV/s.
Result shows, the prepared catalyst of fuel batter with proton exchange film of the present invention is compared with using the catalyst of fuel batter with proton exchange film that Johnson Matthey company produces, and peak current density increases by 18%.
Chloroplatinic acid/ruthenium hydrochloride is dissolved in the aqueous solution that is mixed with 1L in deionized water, wherein in solution, the content of platinum ion and ruthenium ion is 2g/L, the mol ratio of platinum and ruthenium is 1:1, add carbon black to adsorb in chloroplatinic acid/ruthenium hydrochloride solution, the carrying capacity that makes chloroplatinic acid/ruthenium hydrochloride on carbon black is 30wt%, ultrasonic wave stirs, obtain suspension, heat described suspension to 50 ℃, kept 1 hour, regulate the pH value to 7.5 of suspension with ammonia spirit, suspension was stirred 30 minutes under Ultrasonic Conditions, obtain precursor liquid.
Get the 0.6g sodium borohydride, add in the 10mL deionized water, be mixed with sodium borohydride solution.
Described precursor liquid is poured into rapidly in sodium borohydride solution, carried out simultaneously ultrasonic agitation, kept 1 hour, get mixed liquor.
With standing 1 hour of mixed liquor, filter, obtain solid matter, adopt deionized water that described solid matter is washed, until in the cleaning solution after washing without Cl
-Till, the solid matter after washing 80 ℃ of lower vacuum drying, is obtained catalyst of fuel batter with proton exchange film.
Produce to 50 μ L Aldrich companies, mass concentration is to add the above-mentioned catalyst of fuel batter with proton exchange film of 5mg in 5% Nafion solution, ultrasonic wave disperses 30min, obtains mixed solution; Get the 10 described mixed solutions of μ L and drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode.
With the said film electrode, with the Ag/AgCl electrode as reference electrode, Pt sheet as the three-electrode system that electrode is formed, carry out cyclic voltammetry in the methanol solution through the sulfuric acid of the 0.5mol/L of nitrogen deoxygenation and 0.5mol/L, sweep speed is 20mV/s.
Comparative Examples 5
Produce to 50 μ LAldrich companies, mass concentration is the catalyst of fuel batter with proton exchange film that adds 5mg Johnson Matthey company to produce in 5% Nafion solution, ultrasonic wave disperses 30min, obtains mixed solution; Get the 10 described mixed solutions of μ L and drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode.
With the said film electrode, with the Ag/AgCl electrode as reference electrode, Pt sheet as the three-electrode system that electrode is formed, carry out cyclic voltammetry in the methanol solution through the sulfuric acid of the 0.5mol/L of nitrogen deoxygenation and 0.5mol/L, sweep speed is 20mV/s.
Result shows, the prepared catalyst of fuel batter with proton exchange film of the present invention is compared with using the catalyst of fuel batter with proton exchange film that Johnson Matthey company produces, and peak current density increases by 16%.
Embodiment 6
Chloroplatinic acid/ruthenium hydrochloride is dissolved in the aqueous solution that is mixed with 1L in deionized water, wherein in solution, the content of platinum ion and ruthenium ion is 10g/L, the mol ratio of platinum and ruthenium is 1:1, add carbon black to adsorb in chloroplatinic acid/ruthenium hydrochloride solution, the carrying capacity that makes chloroplatinic acid/ruthenium hydrochloride on carbon black is 75wt%, ultrasonic wave stirs, obtain suspension, heat described suspension to 50 ℃, kept 1 hour, regulate the pH value to 10.5 of suspension with ammonia spirit, suspension was stirred 30 minutes under Ultrasonic Conditions, obtain precursor liquid.
Get the 5g sodium borohydride, add in the 10mL deionized water, be mixed with sodium borohydride solution.
Described precursor liquid is poured into rapidly in sodium borohydride solution, carried out simultaneously ultrasonic agitation, kept 1 hour, get mixed liquor.
With standing 1 hour of mixed liquor, filter, obtain solid matter, adopt deionized water that described solid matter is washed, until in the cleaning solution after washing without Cl
-Till, the solid matter after washing 80 ℃ of lower vacuum drying, is obtained catalyst of fuel batter with proton exchange film.
Produce to 50 μ L Aldrich companies, mass concentration is to add the above-mentioned catalyst of fuel batter with proton exchange film of 5mg in 5% Nafion solution, ultrasonic wave disperses 30min, obtains mixed solution; Get the 10 described mixed solutions of μ L and drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode.
With the said film electrode, with the Ag/AgCl electrode as reference electrode, Pt sheet as the three-electrode system that electrode is formed, carry out cyclic voltammetry in the methanol solution through the sulfuric acid of the 0.5mol/L of nitrogen deoxygenation and 0.5mol/L, sweep speed is 20mV/s.
Comparative Examples 6
Produce to 50 μ L Aldrich companies, mass concentration is the catalyst of fuel batter with proton exchange film that adds 5mg Johnson Matthey company to produce in 5% Nafion solution, ultrasonic wave disperses 30min, obtains mixed solution; Get the 10 described mixed solutions of μ L and drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode.
With the said film electrode, with the Ag/AgCl electrode as reference electrode, Pt sheet as the three-electrode system that electrode is formed, carry out cyclic voltammetry in the methanol solution through the sulfuric acid of the 0.5mol/L of nitrogen deoxygenation and 0.5mol/L, sweep speed is 20mV/s.
Result shows, the prepared catalyst of fuel batter with proton exchange film of the present invention is compared with using the catalyst of fuel batter with proton exchange film that Johnson Matthey company produces, and peak current density increases by 31%.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. the preparation method of a catalyst of fuel batter with proton exchange film comprises the following steps:
A) noble metal halide solution and carbon black are mixed, carry out ultrasonic wave behind adjust pH to 2.5 ~ 10.5 and stir, obtain precursor liquid;
Described noble metal halide is platinum halide or platinum halide and the halid mixture of ruthenium;
B) described precursor liquid is added in sodium borohydride solution, carry out obtaining mixed liquor after ultrasonic wave stirs;
C) described mixed liquor is standing, filter, washing and dry, obtain catalyst of fuel batter with proton exchange film.
2. preparation method according to claim 1, is characterized in that, described platinum halide is one or more in chloroplatinic acid, platinic sodium chloride, potassium chloroplatinate, bromoplatinic acid and iodine platinic acid; Described ruthenium halide is one or more in ruthenium trichloride, ruthenium hydrochloride sodium, ruthenium hydrochloride potassium, bromine ruthenic acid and iodine ruthenic acid.
3. preparation method according to claim 1, is characterized in that, the concentration of the middle precious metal ion of described noble metal halide solution is 0.5g/L ~ 10g/L.
4. preparation method according to claim 1, is characterized in that, described steps A) in, ammoniacal liquor adjust pH to 2.5 ~ 10.5 adopted.
5. preparation method according to claim 1, is characterized in that, steps A) described in the mass ratio of carbon black and described noble metal halide be 100:(20 ~ 75).
6. preparation method according to claim 1, is characterized in that, the concentration of described sodium borohydride is 10g/L ~ 100g/L.
7. preparation method according to claim 1, is characterized in that, the mol ratio of described sodium borohydride and noble metal halide is (2 ~ 10): 1.
8. preparation method according to claim 1, is characterized in that, the volume ratio of described sodium borohydride and noble metal halide solution is (0.0007 ~ 0.8): 1.
9. preparation method according to claim 1, is characterized in that, described step B) the ultrasonic wave mixing time be 0.5 ~ 1h.
10. preparation method according to claim 1, is characterized in that, described steps A) the ultrasonic wave mixing time be 0.5 ~ 1h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111465447A (en) * | 2017-10-23 | 2020-07-28 | 贺利氏阿姆洛伊技术有限公司 | Method for preparing supported platinum particles |
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| GB957883A (en) * | 1962-02-02 | 1964-05-13 | Herbert Charles Brown | New active platinum-group metal catalysts |
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| GB957883A (en) * | 1962-02-02 | 1964-05-13 | Herbert Charles Brown | New active platinum-group metal catalysts |
| US6602630B1 (en) * | 2000-03-14 | 2003-08-05 | The Electrosynthesis Company, Inc. | Membrane electrode assemblies for electrochemical cells |
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| CN111465447A (en) * | 2017-10-23 | 2020-07-28 | 贺利氏阿姆洛伊技术有限公司 | Method for preparing supported platinum particles |
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Application publication date: 20130508 Assignee: SHANDONG JINKELI POWER SOURCES TECHNOLOGY CO.,LTD. Assignor: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES Contract record no.: X2022220000014 Denomination of invention: A preparation method of catalyst for proton exchange membrane fuel cell Granted publication date: 20150114 License type: Common License Record date: 20220927 |
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