CN101916867A - Transmission metal-polythiophene-carbon composite catalytic material and preparation method thereof - Google Patents
Transmission metal-polythiophene-carbon composite catalytic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transmission metal-polythiophene-carbon composite catalytic material and a preparation method thereof and aims to provide an air electrode catalytic material which contains transmission metal and sulfur, can work under high current density and has low voltage loss, simple preparation method and wide and cheap raw material resources and a preparation method thereof. The preparation method comprises the following steps: carrying out chemical oxidative polymerization on carbon black, a thiophene monomer and an oxidant in an acid medium to prepare PTh-C; and adding distilled water to the prepared PTh-C to prepare suspension, adding transition metal nitrate solution to the suspension to react in the constant temperature water bath at 75-80 DEG C for 1-2h under return flow agitation, then adding full quantity of reducing agents to reduce the metal ions and carrying out pumping filtration, washing and drying to obtain a solid product, namely the catalytic material. The transition metal and the polythiophene can form a composite material with a large number of M-S2 reactive sites by being combined, thus having catalytic action on oxygen reduction. The catalytic material has wide raw material resources and can lower the production cost.
Description
Technical field
The present invention relates to electrochemical field, in particular, relate to a kind of transmission metal-polythiophene fen-carbon composite catalytic material that is used for the fuel battery air electrode and preparation method thereof.
Background technology
The positive pole reaction of fuel cell all is the reduction reaction of oxygen.Directly utilizing airborne oxygen is air electrode as the fuel cell anode of oxidant.The reduction reaction process complexity of oxygen, dynamics is slow, is the major part of fuel battery voltage loss.The performance of air electrode directly determines the size of voltage, electric current and the power of battery.Catalysis material is the key technology of air electrode, fuel cell.
At present, platinum metal is the most effective anodal catalysis material in the low-temperature fuel cell, but that the platinum group noble metal is made the catalysis material cost is too high, and resource-constrained can not satisfy the needs of large-scale application.With transition metal such as Fe, Co, Ni, Mn is that all kinds of more cheap catalysis material of active component obtains extensive studies, and the composite oxides that wherein have perovskite, a spinel structure show excellent catalytic performance to oxygen reduction reaction and receive much concern.But metal oxide stability in some media is not strong, and application is restricted, and metal sulfide or nitride may have superior performance.
According to respiratory and photosynthetic basic research, in the life entity structure (M-S, M-N, M represents metal) that the material with catalytic action has metal ion and sulphur or nitrogen Cheng Jian is separated out in hydrogen reduction and oxygen.M-S, M-N may be the catalytic activity positions, and the sulfide of transition metal and nitride have the catalysis potentiality.
Summary of the invention
The object of the present invention is to provide a kind of catalysis material that contains transition metal and sulphur, can work under high current density, the loss of voltage is little, and the preparation method is simple, air electrode catalysis material that raw material resources is extensively cheap again and preparation method thereof.
The present invention is achieved through the following technical solutions:
A kind of transmission metal-polythiophene fen-carbon composite catalytic material that is used for the fuel battery air electrode, it is characterized in that, this catalysis material is carrier with the carbon black, and the active component of catalysis material is the composite material of transition metal and polythiophene, and described transition metal is any among Co, Fe, the Mn.The quality percentage composition of each element is in the catalysis material: carbon is 80-85%, and transition metal is 9%-15%, and sulphur is 0.3%-1.5%, the oxygen of surplus and other elements.Described carbon black can be selected acetylene black or VulcanXC-72 for use, perhaps uses by VulcanXC-72 and acetylene black according to the mixture of mass ratio as 1:1.
A kind of preparation method who is used for the transmission metal-polythiophene fen-carbon composite catalytic material of fuel battery air electrode is characterized in that, comprises the steps:
(1) carbon black, thiophene monomer, oxidant chemical oxidising polymerisation in acid medium is made PTh-C; Wherein, the mass ratio between carbon black, thiophene monomer, the oxidant is 3:2:0.5-1.5, and acid medium is a glacial acetic acid, and the temperature of chemical oxidising polymerisation is 0-30 ℃, and the time is 3-6 hour;
(2) the PTh-C adding distil water with step (1) preparation is made into suspension, and transition metal nitrate solution is joined in the suspension, reacts 1-2h under the backflow stirring condition in 75-80 ℃ of water bath with thermostatic control.The transition metal nitrate addition is that every 1g PTh-C adds 0.003 mol; Add the capacity reducing agent again and make the metal ion reduction, suction filtration, washing, dry gained solid product M-PTh-C are catalysis material then; Described transition metal is any among Co, Fe, the Mn.The quality percentage composition of each element is in the catalysis material: carbon is 80-85%, and transition metal is 9%-15%, and sulphur is 0.3%-1.5%, the O of surplus and other elements.
Described carbon black is acetylene black or VulcanXC-72 or is the mixture of 1:1 according to mass ratio by VulcanXC-72 and acetylene black.
Described oxidant is any in ammonium persulfate, potassium permanganate, the hydrogen peroxide.
Described reducing agent is any in potassium borohydride, sodium borohydride, the hydrazine.
The present invention compared with prior art has following advantage:
1, (PTh is a kind of conducting polymer polythiophene) to polythiophene, has similar porphyrin armaticity circulus, on ring sulphur atom is arranged simultaneously.Transition metal is combined with polythiophene, can form composite material, thereby hydrogen reduction is had catalytic action with a large amount of M-S2 activity sites.
2, catalysis material of the present invention can be exported big operating voltage than under the high current density, and stable performance, and the loss of voltage is little.
3, the used raw material resources of catalysis material of the present invention is extensive, cheap, can reduce production costs.
4, preparation method of the present invention is simple, and process is controlled easily.
Description of drawings
The hydrogen reduction polarization curve that Fig. 1, two kinds of electrodes that prepare with the Co-PTh-C among 5%Pt/C and the embodiment 1 obtain in air atmosphere, 6mol/L KOH medium;
The zinc-air battery of Fig. 2, the electrode assembling made from the Co-PTh-C among the embodiment 1 is with 60mA/cm
2The constant-current discharge curve;
The TEM photo of the Co-PTh-C compound catalyze material that Fig. 3, embodiment 1 obtain;
The TEM photo of the Co-PTh-C compound catalyze material that Fig. 4, embodiment 2 obtain;
Make the ORR polarization curve that the test of Co-PTh-C gas-diffusion electrode obtains by different oxidants among Fig. 5, the embodiment 1-3;
Fig. 6,20 ℃ and 0 ℃ make the ORR polarization curve that the test of Co-PTh-C gas-diffusion electrode obtains;
Fig. 7, different central metal M make the ORR polarization curve that the test of M-PTh-C gas-diffusion electrode obtains.
Embodiment
(1) is that the glacial acetic acid of 1mol/L joins in the 30mL deionized water with 1.25mL concentration, adds acetylene black 3g again, stir the abundant mixing of 15min, add thiophene 2g again, stir 10min again, add ammonium persulfate 0.8g then, stirring reaction 6h under the ice-water bath.The thiophene polymerization under oxidation that is adsorbed in the acetylene black surface makes PTh-C.
(2) take by weighing the PTh-C 1g that obtains, adding distil water is made into the PTh-C suspension of 40g/L and pours in the three-neck flask.Take by weighing cobalt nitrate (Co (NO
3)
26H
2O) 0.89g, adding distil water are made into the cobalt nitrate solution of 0.25mol/L, and cobalt nitrate solution is slowly joined in the three-neck flask, and ultrasonic wave is down auxiliary, reacts 1h under the backflow stirring condition in 75 ℃ of waters bath with thermostatic control.Take by weighing 2.14g potassium borohydride and 0.10g NaOH, add the potassium borohydride alkaline solution that the 125mL deionized water is made into 0.32mol/L, the potassium borohydride alkaline solution is slowly dripped to three-neck flask, reach 11.4 until the pH value of solution value, keep 30 min, pH is constant, and explanation reacts completely.Suction filtration, washing, 75 ℃ of dry gained solid products are Co-PTh-C then.Wherein the content of each element is: C is 80.51%, and Co is 13.6%, and S is 1.41%, and O and other elements are 4.48%.
The Co-PTh-C that obtains is made into electrode according to a conventional method, the hydrogen reduction polarization curve that in air atmosphere, 6mol/L KOH medium, obtains shown in (b) among Fig. 1, at current potential be-the 0.2V condition under, the current density of Co-PTh-C electrode reaches 160mA/cm
2
With the mass fraction of 5%Pt/C(Pt is 5%) be made into electrode according to a conventional method, the hydrogen reduction polarization curve that in air atmosphere, 6mol/L KOH medium, obtains shown in (a) among Fig. 1, at current potential be-the 0.2V condition under, current density is 107mA/cm
2In view of this, the catalytic performance of Co-PTh-C is higher than 5%Pt/C.
The zinc-air battery of the electrode assembling made from the Co-PTh-C that obtains is with 60mA/cm
2The constant-current discharge curve as shown in Figure 2, battery discharge voltage is 1.05V, and discharge platform is stable.
The TEM photo of the Co-PTh-C compound catalyze material that obtains is schemed between the demonstration catalysis material particle size distribution 10nm-30nm as shown in Figure 3, and evenly.
(1) is that the glacial acetic acid of 1mol/L joins in the 30mL deionized water with 1.25mL concentration, adds acetylene black 3g again, stir the abundant mixing of 15min, add the 2g thiophene, stir 10min, add potassium permanganate 1.2g then, stirring reaction 6h under the ice-water bath.The thiophene polymerization under oxidation that is adsorbed in the acetylene black surface makes PTh-C.
(2) take by weighing the PTh-C 1g that obtains, adding distil water is made into the PTh-C suspension of 40g/L and pours in the three-neck flask.Take by weighing cobalt nitrate (Co (NO3) 26H2O) 0.89g, adding distil water is made into the cobalt nitrate solution of 0.25mol/L, and cobalt nitrate solution is slowly joined in the three-neck flask, and ultrasonic wave is down auxiliary, reacts 1h under the backflow stirring condition in 80 ℃ of waters bath with thermostatic control.Take by weighing 2.14g potassium borohydride and 0.10g NaOH, add the potassium borohydride alkaline solution that the 125mL deionized water is made into 0.32mol/L, the potassium borohydride alkaline solution is slowly dripped to three-neck flask, reach 11.3 until the pH value of solution value, keep 30 min, pH is constant, and explanation reacts completely.Suction filtration, washing, 75 ℃ of dry gained solid products are Co-PTh-C then.Wherein the content of each element is: C is 81.70%, and Co is 11.21%, and S is 0.87%, and O and other elements are 6.22%.The TEM photo of the Co-PTh-C compound catalyze material that obtains as shown in Figure 4.
Embodiment 3
(1) is that the glacial acetic acid of 1mol/L joins in the 30mL deionized water with 1.25mL concentration, adds acetylene black 3g again, stir the abundant mixing of 15min, add the 2g thiophene again, stir 10min again, add the 5mL mass percent concentration then and be 10% hydrogenperoxide steam generator, 0 ℃ of following stirring reaction 5h.The thiophene polymerization under oxidation that is adsorbed in the acetylene black surface makes PTh-C.
(2) take by weighing the PTh-C 1g that obtains, adding distil water is made into the PTh-C suspension of 40g/L and pours in the three-neck flask.Take by weighing cobalt nitrate (Co (NO3) 26H2O) 0.89g, adding distil water is made into the cobalt nitrate solution of 0.25mol/L, and cobalt nitrate solution is slowly joined in the three-neck flask, and ultrasonic wave is down auxiliary, reacts 1h under the backflow stirring condition in 80 ℃ of waters bath with thermostatic control.Take by weighing 2.14g potassium borohydride and 0.10g NaOH, add the potassium borohydride alkaline solution that the 125mL deionized water is made into 0.32mol/L, the potassium borohydride alkaline solution is slowly dripped to three-neck flask, reach 11.5 until the pH value of solution value, keep 30 min, pH is constant, and explanation reacts completely.Suction filtration, washing, 75 ℃ of dry gained solid products are Co-PTh-C then.Wherein the content of each essential element is: C is 83.39%, and Co is 9.73%, and S is 0.38%, and O and other elements are 6.5%.
Embodiment 4
(1) is that the glacial acetic acid of 1mol/L joins in the 30mL deionized water with 1.25mL concentration, adds acetylene black 3g again, stir the abundant mixing of 15min, add thiophene 2g again, stir 10min again, add 5mL mass percent concentration 10% hydrogenperoxide steam generator then, 20 ℃ of following stirring reaction 5h.The thiophene polymerization under oxidation that is adsorbed in the acetylene black surface makes PTh-C.
(2) take by weighing the PTh-C 1g that obtains, adding distil water is made into the PTh-C suspension of 40g/L and pours in the three-neck flask.Take by weighing cobalt nitrate (Co (NO3) 26H2O) 0.89g, adding distil water is made into the cobalt nitrate solution of 0.25mol/L, and cobalt nitrate solution is slowly joined in the three-neck flask, and ultrasonic wave is down auxiliary, reacts 1h under the backflow stirring condition in 80 ℃ of waters bath with thermostatic control.Take by weighing 2.14g potassium borohydride and 0.10g NaOH, add the potassium borohydride alkaline solution that the 125mL deionized water is made into 0.32mol/L, the potassium borohydride alkaline solution is slowly dripped to three-neck flask, reach 11.2 until the pH value of solution value, keep 30 min, pH is constant, and explanation reacts completely.Suction filtration, washing, 75 ℃ of dry gained solid products are Co-PTh-C then.Wherein the content of each essential element is: C is 81.51%, and Co is 12.6%, and S is 0.98%, and O and other elements are 4.91%.
Embodiment 5
(1) be that the glacial acetic acid of 1mol/L joins in the 30mL deionized water with 1.25mL concentration, the VulcanXC-72 that adds 3g cabot company again, stir the abundant mixing of 15min, add thiophene 2g again, stir 10min again, the hydrogenperoxide steam generator that adds 15mL mass percent concentration 10% then, 20 ℃ of following stirring reaction 4h.The thiophene polymerization under oxidation that is adsorbed in the VulcanXC-72 surface makes PTh-C.
(2) take by weighing the PTh-C 1g that obtains, adding distil water is made into the PTh-C suspension of 40g/L and pours in the three-neck flask.Take by weighing ferric nitrate 1.21g, adding distil water is made into the iron nitrate solution of 0.25mol/L, and iron nitrate solution is slowly joined in the three-neck flask, and ultrasonic wave is down auxiliary, reacts 1h under the backflow stirring condition in 80 ℃ of waters bath with thermostatic control.Take by weighing 1.28g hydrazine and 0.10g NaOH, add the hydrazine alkaline solution that the 125mL deionized water is made into 0.32mol/L, the hydrazine alkaline solution is slowly dripped to three-neck flask, reach 11.0 until the pH value of solution value, keep 30 min, pH is constant, and explanation reacts completely.Suction filtration, washing, 75 ℃ of dry gained solid products are Fe-PTh-C then.Wherein the content of each essential element is: C is 80.51%, and Fe is 14.6%, and S is 1.47%, and O and other elements are 3.42%.
Embodiment 6
(1) be that the glacial acetic acid of 1mol/L joins in the 30mL deionized water with 1.25mL concentration, the VulcanXC-72 and the acetylene black that add by cabot company are the mixture 3g of 1:1 according to mass ratio again, stir the abundant mixing of 15min, add thiophene 2g again, stir 10min again, add ammonium persulfate 0.8g then, 30 ℃ of following stirring reaction 4h.The thiophene polymerization under oxidation that is adsorbed in VulcanXC-72 and acetylene black surface makes PTh-C.
(2) take by weighing the PTh-C 1g that obtains, adding distil water is made into the PTh-C suspension of 40g/L and pours in the three-neck flask.Take by weighing manganese nitrate 0.75g, adding distil water is made into the manganese nitrate solution of 0.25mol/L, and manganese nitrate solution is slowly joined in the three-neck flask, and ultrasonic wave is down auxiliary, reacts 1h under the backflow stirring condition in 80 ℃ of waters bath with thermostatic control.Take by weighing 1.51g sodium borohydride and 0.10g NaOH, add the sodium borohydride alkaline solution that the 125mL deionized water is made into 0.32mol/L, the sodium borohydride alkaline solution is slowly dripped to three-neck flask, reach 11.4 until the pH value of solution value, keep 30 min, pH is constant, and explanation reacts completely.Suction filtration, washing, 75 ℃ of dry gained solid products are Mn-PTh-C then.Wherein the content of each essential element is: C is 84.37%, and Mn is 9.1%, and S is 0.34%, and O and other elements are 6.19%.
Fig. 5 makes the ORR polarization curve that the test of Co-PTh-C gas-diffusion electrode obtains by different oxidants among the embodiment 1-3.Wherein, (a) be that potassium permanganate is as oxidant, (b) be that hydrogen peroxide is as oxidant, (c) be that ammonium persulfate is as oxidant, be presented among the figure under current potential-0.2V, the Co-PTh-C electrode current density that obtains as oxidant with potassium permanganate, hydrogen peroxide, ammonium persulfate is respectively 110mAcm
-2, 149mAcm
-2, 158mAcm
-2Be the hydrogen reduction performance ammonium persulfate of the catalysis material Co-PTh-C that makes of different oxidants〉hydrogen peroxide〉potassium permanganate.
Fig. 6 is that 20 ℃ (embodiment 4) and 0 ℃ (embodiment 3) make the ORR polarization curve that the test of Co-PTh-C gas-diffusion electrode obtains.As can be seen from the figure when current potential-0.2V, room temperature (20 ℃) and 0 ℃ make Co-PTh-C gas-diffusion electrode current density and are respectively 71mA/cm2,96mA/cm
2
Fig. 7 is that different central metal M make the ORR polarization curve that the test of M-PTh-C gas-diffusion electrode obtains.(a) be Mn-PTh-C(embodiment 6), (b) for Fe-PTh-C(embodiment 5), (c) be Co-PTh-C(embodiment 1).As can be seen from the figure when current potential be-during 0.20V, the current density of Mn-PTh-C, Fe-PTh-C, Co-PTh-C electrode is respectively 83mAcm
-2, 102mAcm
-2, 158mAcm
-2
Claims (6)
1. transmission metal-polythiophene fen-carbon composite catalytic material that is used for the fuel battery air electrode, it is characterized in that, this catalysis material is carrier with the carbon black, the active component of catalysis material is the composite material of transition metal and polythiophene, described transition metal is any among Co, Fe, the Mn, and the quality percentage composition of each element is in the catalysis material: carbon is 80-85%, and transition metal is 9%-15%, sulphur is 0.3%-1.5%, the oxygen of surplus and other elements.
2. the transmission metal-polythiophene fen-carbon composite catalytic material that is used for the fuel battery air electrode according to claim 1, it is characterized in that described carbon black is acetylene black or VulcanXC-72 or is the mixture of 1:1 according to mass ratio by VulcanXC-72 and acetylene black.
3. the described preparation method who is used for the transmission metal-polythiophene fen-carbon composite catalytic material of fuel battery air electrode of claim 1 is characterized in that, comprises the steps:
(1) carbon black, thiophene monomer, oxidant chemical oxidising polymerisation in acid medium is made PTh-C; Wherein, the mass ratio between carbon black, thiophene monomer, the oxidant is 3:2:0.5-1.5, and acid medium is a glacial acetic acid, and the temperature of chemical oxidising polymerisation is 0-30 ℃, and the time is 3-6 hour;
(2) the PTh-C adding distil water with step (1) preparation is made into suspension, and transition metal nitrate solution is joined in the suspension, reacts 1-2h under the backflow stirring condition in 75-80 ℃ of water bath with thermostatic control; The transition metal nitrate addition is that every 1g PTh-C adds 0.003 mol; Add the capacity reducing agent again and make the metal ion reduction, suction filtration, washing, dry gained solid product M-PTh-C are catalysis material then; Described transition metal is any among Co, Fe, the Mn.
4. the preparation method who is used for the transmission metal-polythiophene fen-carbon composite catalytic material of fuel battery air electrode according to claim 3, it is characterized in that described carbon black is acetylene black or VulcanXC-72 or is the mixture of 1:1 according to mass ratio by VulcanXC-72 and acetylene black.
5. the preparation method who is used for the transmission metal-polythiophene fen-carbon composite catalytic material of fuel battery air electrode according to claim 3 is characterized in that described oxidant is any in ammonium persulfate, potassium permanganate, the hydrogen peroxide.
6. the preparation method who is used for the transmission metal-polythiophene fen-carbon composite catalytic material of fuel battery air electrode according to claim 3 is characterized in that described reducing agent is any in potassium borohydride, sodium borohydride, the hydrazine.
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| CN103326041A (en) * | 2013-06-19 | 2013-09-25 | 厦门大学 | Oxygen reduction electrocatalyst and preparation method thereof |
| CN104291433A (en) * | 2014-10-15 | 2015-01-21 | 济南大学 | Method for treating organic waste water based on polythiophene/zero-valent iron composite material activated molecule oxygen |
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| US20070082253A1 (en) * | 2005-10-06 | 2007-04-12 | The Regents Of The University Of California | Metal-polymer composite catalysts |
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| US20070082253A1 (en) * | 2005-10-06 | 2007-04-12 | The Regents Of The University Of California | Metal-polymer composite catalysts |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326041A (en) * | 2013-06-19 | 2013-09-25 | 厦门大学 | Oxygen reduction electrocatalyst and preparation method thereof |
| CN103326041B (en) * | 2013-06-19 | 2015-03-25 | 厦门大学 | Oxygen reduction electrocatalyst and preparation method thereof |
| CN104291433A (en) * | 2014-10-15 | 2015-01-21 | 济南大学 | Method for treating organic waste water based on polythiophene/zero-valent iron composite material activated molecule oxygen |
| CN104291433B (en) * | 2014-10-15 | 2016-03-02 | 济南大学 | A kind of method based on Polythiophene/zero-valent iron composite material activate molecular oxygen process organic waste water |
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Application publication date: 20101215 |