CN114864973A - Anti-reversal catalyst, preparation method thereof and fuel cell - Google Patents
Anti-reversal catalyst, preparation method thereof and fuel cell Download PDFInfo
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- CN114864973A CN114864973A CN202210522666.8A CN202210522666A CN114864973A CN 114864973 A CN114864973 A CN 114864973A CN 202210522666 A CN202210522666 A CN 202210522666A CN 114864973 A CN114864973 A CN 114864973A
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- 239000000446 fuel Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 109
- 229910002849 PtRu Inorganic materials 0.000 claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 41
- 239000000956 alloy Substances 0.000 claims abstract description 41
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 49
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- 238000002156 mixing Methods 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- 238000005121 nitriding Methods 0.000 claims description 18
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- 239000002253 acid Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
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- 238000001354 calcination Methods 0.000 claims description 12
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
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- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 5
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
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- 230000003197 catalytic effect Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
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- 239000001301 oxygen Substances 0.000 description 6
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- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical group O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a catalyst for resisting reversal pole, a preparation method thereof and a fuel cell, wherein the catalyst for resisting reversal pole comprises TiN-TiO 2 Carrier and carrier loaded on TiN-TiO 2 Active component on a support, said TiN-TiO 2 In-situ growth of TiN in a carrier on TiO 2 The active component includes a PtRu alloy, and the molar ratio of Pt to Ru in the PtRu alloy is 100:1 or less. The invention takes PtRu alloy as an active component, TiN-TiO 2 Is used as a carrier to obtain the anti-reversal catalyst, the Ru element with specific content can improve the integral water electrolysis performance of the catalyst, and TiN grows on TiO in situ 2 The surface of (2) and the two have synergistic effect to promote the conductivity and stability of the catalyst, and effectively get rid of the carbon corrosion caused by the reverse electrode of the fuel cell, thereby protecting the structure and performance of the catalyst layer of the fuel cell, improving the durability of the fuel cell and promoting the safety performance of the cell.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and relates to an anti-reversal catalyst, a preparation method thereof and a fuel cell.
Background
In recent years, the field of clean energy is being vigorously developed, and a Proton Exchange Membrane Fuel Cell (PEMFC) is a device capable of directly converting chemical energy into electric energy, and has attracted much attention in the field of clean energy due to its advantages of no pollution, high energy conversion efficiency, rapid start at room temperature, etc., but the durability and cost of PEMFC are still barriers to large-scale commercialization. The membrane electrode, which is a key component of PEMFCs, has properties that largely determine the performance of the cell, and the importance of the catalyst, which serves as the basis of the membrane electrode, is conceivable. At present, a catalytic layer of a membrane electrode is mainly formed by spraying Pt/C catalyst and Nafion ionomer on a proton exchange membrane, is called as 'CCM', and is shaped like a sandwich structure. The catalyst layer is the main reaction site of hydrogen and oxygen, hydrogen is oxidized in the anode catalyst layer to generate protons and electrons, and the protons are transferred to the cathode through the proton exchange membrane so as to be able to react with oxygen.
When the PEMFC operates under a complicated working condition, such as rapid load change, start/stop, low-temperature start, etc., the problem of insufficient fuel may occur, and at this time, the catalytic layer cannot perform hydrogen oxidation reaction to provide protons and electrons, and other reactions such as water electrolysis and carbon corrosion reaction are required to maintain charge balance, so that the anode potential is higher than the cathode, the battery voltage has a negative value, and the voltage is continuously reduced, which is "reverse polarity". The opposite pole of the battery can seriously damage the catalytic layer and the gas diffusion layer, thereby affecting the performance and durability of the battery and causing safety accidents in serious cases.
At present, researchers monitor the battery condition through a system control strategy to prevent the occurrence of reverse polarity; however, such system control strategies add complexity and cost to the battery system, and both of these strategies "palliative and non-radical" have the phenomenon of pole reversal already occurring when the battery finds an abnormality. Therefore, researchers have conducted anti-reversal studies on materials such as using a non-carbon support, introducing an electrolytic water catalyst into a catalytic layer, and the like.
CN111082078A discloses a preparation method of a high-performance and anti-reverse-polarity membrane electrode assembly, which adds an electrolyzed water catalyst into a catalyst slurry, and sprays the catalyst slurry onto a proton exchange membrane, so as to effectively alleviate the damage caused by reverse polarity. However, the direct addition of catalyst particles easily causes agglomeration, masking the active sites of Pt. CN111029599A discloses a fuel cell anti-reversal catalyst and a preparation method thereof, wherein the catalyst is iridium oxide composite Ni-doped titanium dioxide, the anti-reversal additive can prolong the electrolytic water reaction time during reversal, but the performance of the cell can be affected due to poor conductivity of metal oxide, and severe mass transfer polarization occurs under high electric density. In addition, the preparation process of the catalyst is complicated, hydrogen is required to be reduced at high temperature, and certain potential safety hazard exists.
Therefore, it is highly desirable to provide a fuel cell anti-reversal catalyst with good conductivity, stability and durability, so as to improve the safety performance of the fuel cell.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an anti-reversal catalyst, a preparation method thereof and a fuel cell. The invention takes PtRu alloy as an active component and TiN-TiO 2 Is used as a carrier to obtain the anti-reversal catalyst, the Ru element with specific content can improve the integral water electrolysis performance of the catalyst, and TiN grows on TiO in situ 2 The surface of (2) and the two have synergistic effect to promote the conductivity and stability of the catalyst, and effectively get rid of the carbon corrosion caused by the reverse electrode of the fuel cell, thereby protecting the structure and performance of the catalyst layer of the fuel cell, improving the durability of the fuel cell and promoting the safety performance of the cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a counter-electrode-resistant catalyst comprising TiN-TiO 2 Carrier and supported on said TiN-TiO 2 Active component on a support, said TiN-TiO 2 In-situ growth of TiN in a carrier on TiO 2 The active component includes a PtRu alloy, and the molar ratio of Pt to Ru in the PtRu alloy is 100:1 or less.
In the present invention, the molar ratio of Pt and Ru in the PtRu alloy is 100:1 or less, and may be, for example, 0.05:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 30:1, 50:1, 80:1 or 100: 1.
The antipole catalyst of the invention comprises an active component and TiN-TiO 2 Carrier, active component including PtRu alloy. In one aspect, TiN-TiO 2 The use of the carrier solves the problem of carbon corrosion from the source, and the TiN improves the TiO 2 Conductivity of the support, TiO 2 The oxidation resistance of TiN is improved, and the catalyst can obtain optimal conductivity and stability under the synergistic effect of the TiN and the catalyst; meanwhile, TiN is grown in situ on TiO 2 The surface of (2) has good dispersibility, strong binding force and stable structure, can further improve the conductivity and stability of the catalyst, and better plays a role in synergy. On the other hand, when the non-carbon carrier is used, the Ru element is introduced, so that the electrolytic water reaction time in the period of the reverse polarity can be prolonged, the durability of the fuel cell is effectively improved, and meanwhile, the proper proportion of Pt and Ru can give consideration to both the self-catalytic performance and the reverse polarity resisting effect of the catalyst, so that the catalyst is suitable for the application of the fuel cell.
The anti-reversal catalyst can avoid the occurrence of carbon corrosion of the catalyst layer during reversal, prolong the reaction time of electrolyzed water, and improve the conductivity and stability of the cell, thereby protecting the fuel cell and improving the durability of the cell.
In the present invention, for TiN-TiO 2 In-situ growth of TiN in a carrier on TiO 2 The surface of (b) is not particularly limited, and, for example, TiO may be used 2 By nitriding in TiO 2 Growing TiN in situ on the surface of the substrate to obtain TiN-TiO 2 And (3) a carrier.
Preferably, the mole ratio of Pt and Ru in the PtRu alloy is (1-100): 1, preferably (1-6): 1, when the content of Ru is more than the threshold, the catalytic performance of the fuel cell is affected, when the content of Ru is less than the threshold, the anti-reversal performance of the fuel cell is affected, and in the preferred content range, the anti-reversal performance of the catalyst can be further improved while the better performance of the fuel cell is maintained.
Preferably, the TiN-TiO 2 TiN and TiO in carrier 2 The mass ratio of (1) to (3) is (0.01 to 10):1, and may be, for example, 0.01:1, 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, and is preferably (0.2 to 5): 1.
TiN-TiO of the present invention 2 The carrier contains TiN and TiO with proper proportion 2 The two are mixed in a proper proportion, and the conductivity of TiN and TiO can be taken into consideration 2 Thereby achieving better conductivity and stability of the catalyst as a whole.
Preferably, the PtRu alloy and the TiN-TiO 2 The mass ratio of the carrier is (0.1-0.7): 1, for example, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1 or 0.7:1, preferably (0.4-0.7): 1, and the active component PtRu alloy and TiN-TiO 2 The proportion of the carriers is suitable, and the carrier is suitable for commercial application.
In a preferred embodiment of the anti-reverse catalyst of the present invention, the diameter of the PtRu alloy is 1 to 10nm, and may be, for example, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, or 10 nm.
Preferably, the TiN-TiO 2 The carrier is in the shape of a sphere-like shape, and the sphere-like specific surface area is higher, so that the carrier is beneficial to loading and dispersing of active components.
Preferably, the TiN-TiO 2 The carrier has a diameter of 50 to 200nm, and may be, for example, 50nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm or 200 nm.
Preferred spheroidal TiN-TiO of the invention 2 A carrier and further TiN-TiO with proper size 2 The carrier and the PtRu alloy are matched with each other, so that the specific surface area and the dispersity of the catalyst are improved, and the catalyst more suitable for fuel cell application is prepared.
In a second aspect, the present invention provides a method for preparing the anti-reversal catalyst according to the first aspect, the method comprising:
(1) mixing a titanium precursor, an organic solvent and an acid solution, and curing to obtain TiO 2 Gel, mixing the TiO 2 Calcining the gel to obtain TiO 2 A carrier;
(2) subjecting the TiO of the step (1) 2 Nitriding the carrier to obtain TiN-TiO 2 A carrier;
(3) subjecting the TiN-TiO of the step (2) 2 And mixing the carrier, the platinum precursor, the ruthenium precursor and the glycol solution, and performing microwave reduction to obtain the anti-reversal catalyst.
The invention firstly adopts a sol-gel method to prepare TiO 2 Carrying out nitridation reduction on a carrier, and carrying out in-situ nitridation loading of TiN on TiO 2 Preparing to obtain TiN-TiO 2 Support, then on TiN-TiO 2 And loading the PtRu alloy on a carrier by using a microwave-assisted polyol method to obtain the anti-reversal catalyst.
The invention provides a new method for preparing a fuel cell anti-reversal catalyst, which utilizes TiN-TiO 2 The carrier replaces a carbon source, and the prepared anti-reversal catalyst is applied to the fuel cell, so that the excellent initial performance of the cell is maintained, and the tolerance of the reversal of the cell is improved; at the same time, TiN-TiO 2 In-situ growth of TiN in a carrier on TiO 2 And the combination property of the two is good, the structure is more stable, the synergistic effect is better, the load of active components is more facilitated, and the performance attenuation of the battery after the electrode reversal is reduced. The preparation method of the invention has simple operation, short time consumption, low cost of the catalyst carrier material, wide source, large-scale production and use and better anti-reversal effect than the prior art.
Preferably, in the step (1), the titanium precursor is dissolved in the organic solvent, and the acid solution is added after the titanium precursor is fully dissolved.
Preferably, the titanium precursor in step (1) includes any one or a combination of at least two of tetrabutyl titanate, titanium tetrachloride, titanium trichloride and titanium sulfate, and may be, for example, a combination of tetrabutyl titanate and titanium tetrachloride, a combination of titanium trichloride and titanium sulfate, a combination of tetrabutyl titanate, titanium tetrachloride, titanium trichloride and titanium sulfate, or the like.
Preferably, the organic solvent in step (1) includes any one or a combination of at least two of isopropanol, ethylene glycol and glycerol, and may be, for example, a combination of isopropanol and ethylene glycol, a combination of ethylene glycol and glycerol, a combination of isopropanol, ethylene glycol and glycerol, or the like.
Preferably, the acid solution of step (1) comprises nitric acid and/or hydrochloric acid.
Preferably, the curing temperature in the step (1) is 30 to 80 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃ and the like.
Preferably, the curing time in the step (1) is 4-24 h, for example, 4h, 6h, 10h, 14h, 18h, 20h, 22h or 24h, etc.
Preferably, the temperature of the calcination in the step (1) is 300 to 600 ℃, for example, 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃.
Preferably, the calcination time in step (1) is 2-8 h, for example, 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc.
Preferably, after the calcination in step (1), the obtained TiO is also added 2 Grinding the carrier to obtain TiO 2 And (3) powder.
As a preferred technical scheme of the preparation method, the temperature of the nitridation in the step (2) is 600-1200 ℃, for example, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or 1200 ℃, when the temperature is lower, TiO is added 2 Is not enough to crystallize and form TiN phase, reduces the conductivity of the material, and can cause TiO when the temperature is higher 2 All nitride is formed into TiN phase, which reduces the oxidation resistance of the material.
Preferably, the nitriding time in the step (2) is 1-8 h, and may be 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h, for example.
Preferably, the gas in the nitriding atmosphere in step (2) is ammonia gas.
Preferably, after the nitriding in the step (2) and before the mixing in the step (3), a grinding operation is further performed.
Preferably, after the mixing and before the microwave reduction in the step (3), nitrogen is further introduced to remove oxygen.
Preferably, after the oxygen removal and before the microwave reduction in the step (3), alkali liquor is further added to adjust the pH value to be more than or equal to 10.
Preferably, the microwave reduction in step (3) is carried out by placing the mixed solution in step (3) in a microwave reactor for reaction.
Preferably, the power of the microwave reactor is 500-1000W, such as 500W, 600W, 700W, 800W, 900W or 1000W.
Preferably, the microwave reduction time in step (3) is 0.5-5 min, for example, 0.5min, 1min, 2min, 3min, 4min or 5 min.
Preferably, the platinum precursor in step (3) includes any one of chloroplatinic acid, potassium chloroplatinate, and platinum acetylacetonate or a combination of at least two of them, and for example, may be a combination of chloroplatinic acid and potassium chloroplatinate, a combination of potassium chloroplatinate and platinum acetylacetonate, a combination of chloroplatinic acid and platinum acetylacetonate, or a combination of chloroplatinic acid, potassium chloroplatinate, and platinum acetylacetonate.
Preferably, the ruthenium precursor in step (3) includes any one of ruthenium trichloride, potassium chlororuthenate and ruthenium acetate or a combination of at least two of them, for example, a combination of ruthenium trichloride and potassium chlororuthenate, a combination of potassium chlororuthenate and ruthenium acetate, a combination of ruthenium trichloride and ruthenium acetate, or a combination of ruthenium trichloride, potassium chlororuthenate and ruthenium acetate.
As a preferable technical scheme of the preparation method of the invention, the preparation method comprises the following steps:
(1) mixing a titanium precursor, an organic solvent and an acid solution, and curing for 4-24 hours in a water bath at the temperature of 30-80 ℃ to obtain TiO 2 Gel, mixing the TiO 2 Drying the gel, and calcining at 300-600 ℃ for 2-8 h to obtain TiO 2 A carrier;
(2) subjecting the TiO of the step (1) 2 Nitriding the carrier for 1-8 h in the atmosphere of ammonia gas at the nitriding temperature of 600-1200 ℃ to obtain TiN-TiO 2 A carrier;
(3) subjecting the TiN-TiO of the step (2) 2 Mixing the carrier, platinum precursor, ruthenium precursor and glycol solution, and placing in a micro-reactorAnd reacting in a wave reactor for 0.5-5 min, wherein the power of the microwave reactor is 500-1000W, and thus obtaining the antipole catalyst.
In a third aspect, the present invention provides a fuel cell comprising the anti-reversal catalyst according to the first aspect in an anode thereof.
The fuel cell of the invention maintains excellent initial performance, improves the anti-reversal capability, reduces the attenuation of the cell performance after reversal, and after 50 times of reversal, 1000mA cm -2 The voltage decay at (a) does not exceed 4.60%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the antipole catalyst of the invention comprises an active component and TiN-TiO 2 Carrier, active component including PtRu alloy. In one aspect, TiN-TiO 2 The use of the carrier solves the problem of carbon corrosion from the source, and TiN grows in situ on TiO 2 The surface of the titanium dioxide has good dispersibility, strong binding force and stable structure, and TiN improves TiO 2 Conductivity of the support, TiO 2 The oxidation resistance of TiN is improved, and the catalyst can obtain optimal conductivity and stability under the synergistic effect of the TiN and the catalyst. On the other hand, when the non-carbon carrier is used, the Ru element is introduced, so that the electrolytic water reaction time in the period of the reverse polarity can be prolonged, the durability of the fuel cell is effectively improved, and meanwhile, the proper proportion of Pt and Ru can give consideration to both the self-catalytic performance and the reverse polarity resisting effect of the catalyst, so that the catalyst is suitable for the application of the fuel cell.
(2) The anti-reversal catalyst can avoid the occurrence of carbon corrosion of a catalyst layer during reversal, prolong the reaction time of electrolyzed water, and improve the conductivity and stability of the cell, thereby protecting a fuel cell and improving the durability of the cell, wherein the cell has 1000mA cm after 50 times of reversal -2 The voltage decay at (a) does not exceed 4.60%.
Drawings
FIG. 1 is a view showing TiN-TiO compound in example 1 of the present invention 2 XRD pattern of the support.
FIG. 2 is a view showing TiN-TiO compound in example 1 of the present invention 2 TEM image of the support.
FIG. 3Is TiN-TiO in example 1 of the present invention 2 CV curves of the carriers before and after 10h potentiostatic test.
FIG. 4 is an I-V curve of the anti-reversal catalyst before and after 50 times of anti-reversal in example 1 of the present invention.
FIG. 5 shows Pt in comparative example 1 of the present invention 3 Ru 1 I-V curves of the/C catalyst before and after 50 antipolarisation.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of an anti-reversal catalyst, which comprises the following steps:
(1) weighing 2.0g of tetrabutyl titanate, dissolving the tetrabutyl titanate in 100mL of ethylene glycol, adding a hydrochloric acid solution after the tetrabutyl titanate is fully dissolved, uniformly mixing, and curing in a water bath at 40 ℃ for 12 hours to obtain TiO 2 Gelling the obtained TiO 2 Drying the gel, and calcining the gel for 6 hours at 450 ℃ in a muffle furnace to obtain TiO 2 Carrier, fully grinding to obtain TiO 2 Powder;
(2) weighing 1.0g of the TiO in the step (1) 2 Putting the powder into a tubular furnace filled with flowing ammonia gas, nitriding and reducing for 4 hours at 800 ℃, and grinding the powder after reaction to obtain TiN-TiO 2 A carrier;
(3) weighing 155mg of TiN-TiO described in the step (2) 2 Putting the carrier into a special container of a microwave reactor, ultrasonically dispersing the carrier in 60mL of glycol solution, adding 3.7mg/mL of chloroplatinic acid solution and 3.9mg/mL of ruthenium trichloride solution under stirring to ensure that the molar ratio of Pt to Ru is 2:1, the sum of the amounts of substances of Pt and Ru is 0.6mmol, introducing nitrogen to remove oxygen for 30min, and then adjusting the pH to 10 by using 2mol/L NaOH solution; and finally, placing the container into a microwave reactor for reduction, wherein the power of the microwave reactor is set to be 800W, the reaction time is 3min, repeatedly washing the obtained reaction product with deionized water, and drying in a drying oven in vacuum to obtain the antipole catalyst, which is marked as Pt 2 Ru 1 /TiN-TiO 2 。
The anti-reverse catalyst Pt prepared in the example 2 Ru 1 /TiN-TiO 2 Including TiN-TiO 2 Carrier and carrier loaded on TiN-TiO 2 PtRu alloy on a carrier, wherein the molar ratio of Pt to Ru in the PtRu alloy is 2:1, and TiN-TiO 2 TiN and TiO in carrier 2 In a mass ratio of 3:2, PtRu alloy and the TiN-TiO 2 The mass ratio of the carrier is 98: 155.
FIG. 1 shows TiN-TiO prepared in this example 2 XRD pattern of the support; FIG. 2 is a view showing that TiN-TiO prepared in this example 2 TEM image of the support, from which TiN-TiO can be seen 2 The carrier is spherical-like in shape and 50-200 nm in diameter.
FIG. 3 is a view showing that TiN-TiO prepared in this example 2 The CV curves of the carrier before and after 10h constant potential test, the test potential was kept at 1.5V, as can be seen from FIG. 3, TiN-TiO before and after constant potential test 2 The CV curve of the carrier has small change, which shows that the carrier has excellent electrochemical stability and can be used for the anode anti-reversal electrode of the fuel cell.
Example 2
The embodiment provides a preparation method of an anti-reversal catalyst, which comprises the following steps:
(1) weighing 2.0g of tetrabutyl titanate, dissolving in 100mL of ethylene glycol, adding a hydrochloric acid solution after fully dissolving, uniformly mixing, and curing in a water bath at 40 ℃ for 12h to obtain TiO 2 Gelling the obtained TiO 2 Drying the gel, and calcining the gel for 6 hours at 450 ℃ in a muffle furnace to obtain TiO 2 Carrier, fully grinding to obtain TiO 2 Powder;
(2) weighing 1.0g of the TiO in the step (1) 2 Putting the powder into a tubular furnace filled with flowing ammonia gas, nitriding and reducing for 4 hours at 800 ℃, and grinding the powder after reaction to obtain TiN-TiO 2 A carrier;
(3) weighing 155mg of TiN-TiO described in the step (2) 2 The carrier is placed into a special container of a microwave reactor, is dispersed in 60mL of glycol solution by ultrasonic dispersion, and is added with 3.7mg/mL of chloroplatinic acid solution and 3.9mg/mL of ruthenium trichloride solution under stirring to ensure that the molar ratio of Pt and Ru is 31, the total metal molar weight is 0.6mmol, then nitrogen is introduced for deoxygenation for 30min, and then 2mol/L NaOH solution is used for adjusting the pH value to 10; and finally, placing the container into a microwave reactor for reduction, wherein the power of the microwave reactor is set to be 800W, the reaction time is 3min, repeatedly washing the obtained reaction product with deionized water, and drying in a drying oven in vacuum to obtain the antipole catalyst, which is marked as Pt 3 Ru 1 /TiN-TiO 2 。
The anti-reverse catalyst Pt prepared in the example 3 Ru 1 /TiN-TiO 2 Including TiN-TiO 2 Carrier and carrier loaded on TiN-TiO 2 PtRu alloy on a carrier, wherein the molar ratio of Pt to Ru in the PtRu alloy is 3:1, and TiN-TiO 2 TiN and TiO in carrier 2 In a mass ratio of 3:2, PtRu alloy and the TiN-TiO 2 The mass ratio of the carrier is 103: 155.
Example 3
The embodiment provides a preparation method of an anti-reversal catalyst, which comprises the following steps:
(1) weighing 2.0g of tetrabutyl titanate, dissolving in 100mL of ethylene glycol, adding a hydrochloric acid solution after fully dissolving, uniformly mixing, and curing in a water bath at 40 ℃ for 12h to obtain TiO 2 Gelling the obtained TiO 2 Drying the gel, and calcining the gel for 6 hours at 450 ℃ in a muffle furnace to obtain TiO 2 Carrier, fully grinding to obtain TiO 2 Powder;
(2) weighing 1.0g of the TiO in the step (1) 2 Putting the powder into a tubular furnace filled with flowing ammonia gas, nitriding and reducing for 4 hours at 800 ℃, and grinding the powder after reaction to obtain TiN-TiO 2 A carrier;
(3) weighing 155mg of TiN-TiO described in the step (2) 2 Putting the carrier into a special container of a microwave reactor, ultrasonically dispersing the carrier in 60mL of glycol solution, adding 3.7mg/mL of chloroplatinic acid solution and 3.9mg/mL of ruthenium trichloride solution under stirring to ensure that the molar ratio of Pt to Ru is 4:1 and the molar weight of total metals is 0.6mmol, introducing nitrogen to remove oxygen for 30min, and adjusting the pH to 10 by using 2mol/L of NaOH solution; finally, the container is placed into a microwave reactor for reduction, wherein the power of the microwave reactor is set to be 800W, the reaction time is 3min, and the obtained product is obtainedRepeatedly washing the reaction product with deionized water, and drying in a drying oven in vacuum to obtain the antipole catalyst, which is marked as Pt 4 Ru 1 /TiN-TiO 2 。
The anti-reverse catalyst Pt prepared in the example 4 Ru 1 /TiN-TiO 2 Including TiN-TiO 2 Carrier and carrier loaded on TiN-TiO 2 PtRu alloy on a support, the molar ratio of Pt to Ru in the PtRu alloy being 4:1, TiN-TiO 2 TiN and TiO in carrier 2 In a mass ratio of 3:2, PtRu alloy and the TiN-TiO 2 The mass ratio of the carrier was 106: 155.
Example 4
The procedure was as in example 1 except that the molar ratio of Pt to Ru in the PtRu alloy was 7: 1.
Example 5
The procedure was as in example 1 except that the molar ratio of Pt to Ru in the PtRu alloy was 0.5: 1.
Example 6
Removing TiN-TiO 2 TiN and TiO in carrier 2 The same as in example 1 except that the mass ratio of (A) to (B) was 0.15: 1.
Example 7
Removing TiN-TiO 2 TiN and TiO in carrier 2 The mass ratio of (A) to (B) was 5.5:1, and the rest was the same as in example 1.
Example 8
Except PtRu alloy and TiN-TiO 2 The procedure of example 1 was repeated except that the carrier mass ratio was 0.3: 1.
Example 9
Except PtRu alloy and TiN-TiO 2 The procedure of example 1 was repeated except that the carrier mass ratio was 0.8: 1.
Example 10
The same procedure as in example 1 was repeated except that the temperature of the nitriding in step (2) was 550 ℃.
Example 11
The same procedure as in example 1 was repeated except that the temperature of the nitriding in step (2) was 1250 ℃.
Comparative example 1
Except that the operation of step (1) or (2) is not performedDirectly replacing TiN-TiO with XC-72(Cabot corporation) 2 Preparation of support to obtain Pt 3 Ru 1 The rest of the catalyst was the same as in example 2.
Comparative example 2
The procedure was as in example 1 except that the molar ratio of Pt to Ru in the PtRu alloy was 120: 1.
Comparative example 3
Directly adding TiN and TiO without carrying out the operations of the steps (1) and (2) 2 Grinding and mixing to obtain TiN-TiO 2 The carrier was the same as in example 1.
TiN and TiO used in this example 2 Purchased from aladdin, all 50-150 nm in size.
And (3) testing the anti-reversal performance: mixing the catalysts prepared in examples 1-11 and comparative examples 1-3 with isopropanol and deionized water to prepare catalyst slurry, spraying the catalyst slurry on a Nafion proton membrane to obtain a fuel cell anode catalyst layer, spraying the catalyst slurry prepared from a Pt/C catalyst on the other side to obtain a cathode catalyst layer, then hot-pressing the cathode catalyst layer and a Gas Diffusion Layer (GDL) to form a Membrane Electrode Assembly (MEA), assembling the MEA into a single cell for testing, wherein the effective area of the MEA is 5cm 2 . The cell reversal is triggered by fuel starvation, namely, under the normal operation condition of the cell, anode hydrogen is replaced by nitrogen, and a power supply is used for outputting 200mA/cm to the cell 2 The anti-reversal performance of the fuel cell is tested, the cut-off voltage is-1V, and after 50 times of reversal, the current of the fuel cell is recorded at 1000mA cm -2 The voltage decay rate of (d) was as shown in table 1.
TABLE 1
As can be seen from the above examples 1 to 11, the present invention uses PtRu alloy as an active component and TiN-TiO 2 As a carrier to obtain the anti-reversal catalystThe Ru element with specific content can improve the integral electrolytic water performance of the catalyst, and TiN grows on TiO in situ 2 The surface and the two have synergistic effect to improve the conductivity and stability of the catalyst, effectively get rid of the carbon corrosion caused by the reversal of the fuel cell, thereby protecting the structure and performance of the catalyst layer of the fuel cell, improving the durability of the fuel cell, and after the cell is reversed for 50 times, the battery has 1000mA cm -2 The voltage attenuation is not more than 4.60%, and the safety performance of the battery is improved.
FIG. 4 shows the anti-reversal catalyst Pt of example 1 2 Ru 1 /TiN-TiO 2 I-V curves before and after 50 times of antipolarization, and as can be seen from the curves before and after 50 times of antipolarization in FIG. 4, 1000mA cm after 50 times of antipolarization -2 The voltage is only attenuated by 0.88%, which shows that the anti-reversal catalyst provided by the invention can effectively reduce the damage of frequent reversal on the performance of the fuel cell.
It is understood from the comparison between example 1 and examples 4 to 5 and comparative example 2 that the most suitable ratio range of Pt and Ru in the PtRu alloy of the anti-reversal catalyst affects the catalytic performance of the fuel cell itself when the Ru content is large, affects the anti-reversal effect when the Ru content is small, the ratio of Pt and Ru in example 4 is large, the ratio of Pt and Ru in comparative example 2 is too large, resulting in a decrease in the anti-reversal effect of the fuel cell, and the ratio of Pt and Ru in example 5 is small, affecting the output performance of the fuel cell itself, decreasing the initial voltage, and thus, the catalyst combination property of example 1 is the best.
As can be seen from the comparison of example 1 with examples 6 to 7, TiN and TiO in the anti-reversal catalyst of the present invention 2 There is the most suitable ratio when TiN and TiO 2 When the mass ratio of (1) to (0.2-5), both conductivity and stability can be achieved; TiO in example 6 2 The content of (A) is too large, which affects the conductivity of the catalyst and thus lowers the output performance of the fuel cell, while the content of TiN in example 7 affects the oxidation resistance of the catalyst and thus the voltage attenuation of example 7 is 3.92%, which is higher than that of example 1; thus, example 1 used appropriate amounts of TiN and TiO 2 Further improves the initial electricity of the catalystCompressive and anti-reversal capabilities.
As can be seen from a comparison of example 1 with examples 8 to 9, the invention employs appropriate amounts of PtRu alloy and TiN-TiO 2 The carrier can further improve the hydrogen oxidation activity and the anti-reversal capacity of the catalyst; in example 8, the PtRu alloy content is low, and although the anti-reversal capability is good, the initial performance of the fuel cell is affected due to the decrease in the mass fraction of Pt, and in example 9, the PtRu alloy content is high, so that the mass fraction of Pt is high, the cost is increased, and the initial performance of the fuel cell is not effectively improved due to the serious catalyst agglomeration. Therefore, the initial performance and the anti-reversal performance of the battery of example 1 were better.
As can be seen from the comparison between example 1 and examples 10-11, the cell initial performance and the anti-reversal performance of the anti-reversal catalyst prepared in the invention when the nitridation temperature is 600-1200 ℃, and the lower nitridation temperature in example 10 can cause TiO 2 The conversion to TiN phase was not successful and the conductivity was poor. Example 11 the higher nitridation temperature resulted in TiO 2 All converted into TiN phase, and the stability is sharply reduced along with the improvement of the conductivity. Thus, the initial performance and the anti-reversal performance of the battery of example 1 were better than those of examples 10 to 11.
FIG. 5 shows Pt of comparative example 1 3 Ru 1 I-V curves of the/C catalyst before and after 50 times of antipolarization resistance, as can be seen from the curves before and after FIG. 5, 1000mA cm after 50 times of antipolarization -2 The voltage was attenuated by 9.0%, which is much higher than 0.88% in example 1 of the present invention, and the attenuation amount was much higher than that in example 2 of the present invention at the same ratio of Pt and Ru, and therefore, carbon corrosion during the reverse polarity could not be effectively prevented and the durability and safety of the fuel cell could not be improved by preparing the catalyst using the conventional carbon support.
As can be seen from the comparison of example 1 with comparative example 3, TiN-TiO was prepared by the sol-gel method and the in-situ nitrogen reduction method of the present invention 2 The carrier is matched with a microwave-assisted polyol method to load the PtRu alloy, so that the prepared anti-reversal catalyst has better initial performance and anti-reversal performance of the battery; in comparative example 3, T is mixed by conventional physical mixing methodiN and TiO 2 Grinding and mixing the two, and synthesizing the two in situ to prepare the TiN-TiO 2 Poor morphology of the support, TiO 2 And TiN, the aggregation is serious, the specific surface area is small, the ability of loading the PtRu alloy is reduced, and the stability of the catalyst is also affected to a certain extent, so that the initial performance and the anti-reversal performance of the battery of example 1 are better than those of comparative example 3.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. An anti-reversal catalyst, characterized in that the anti-reversal catalyst comprises TiN-TiO 2 Carrier and supported on said TiN-TiO 2 Active component on a support, said TiN-TiO 2 In-situ growth of TiN in a carrier on TiO 2 The active component includes a PtRu alloy, and the molar ratio of Pt to Ru in the PtRu alloy is 100:1 or less.
2. The antipole catalyst according to claim 1, wherein the molar ratio of Pt to Ru in the PtRu alloy is (1-100): 1, preferably (1-6): 1;
preferably, the TiN-TiO 2 TiN and TiO in carrier 2 The mass ratio of (0.01-10) to (1), preferably (0.2-5) to (1);
preferably, the PtRu alloy and the TiN-TiO 2 The mass ratio of the carrier is (0.1-0.7): 1, preferably (0.4-0.7): 1.
3. The anti-reverse-polarity catalyst according to claim 1 or 2, wherein the diameter of the PtRu alloy is 1 to 10 nm;
preferably, the TiN-TiO 2 The shape of the carrier is similar to a sphere;
preferably, the TiN-TiO 2 Of carriersThe diameter is 50-200 nm.
4. A method for preparing a catalyst according to any one of claims 1 to 3, characterized in that it comprises:
(1) mixing a titanium precursor, an organic solvent and an acid solution, and curing to obtain TiO 2 Gel, mixing the TiO 2 Calcining the gel to obtain TiO 2 A carrier;
(2) subjecting the TiO of the step (1) 2 Nitriding the carrier to obtain TiN-TiO 2 A carrier;
(3) subjecting the TiN-TiO of the step (2) 2 And mixing the carrier, the platinum precursor, the ruthenium precursor and the glycol solution, and performing microwave reduction to obtain the anti-reversal catalyst.
5. The production method according to claim 4, wherein the titanium precursor in the step (1) comprises any one of tetrabutyl titanate, titanium tetrachloride, titanium trichloride and titanium sulfate or a combination of at least two of them;
preferably, the organic solvent in step (1) comprises any one or a combination of at least two of isopropanol, ethylene glycol and glycerol;
preferably, the acid solution of step (1) comprises nitric acid and/or hydrochloric acid.
6. The preparation method according to claim 4 or 5, wherein the curing temperature in the step (1) is 30-80 ℃;
preferably, the curing time in the step (1) is 4-24 h;
preferably, the calcining temperature in the step (1) is 300-600 ℃;
preferably, the calcining time in the step (1) is 2-8 h.
7. The method according to any one of claims 4 to 6, wherein the temperature of the nitriding in the step (2) is 600 to 1200 ℃;
preferably, the nitriding time in the step (2) is 1-8 h;
preferably, the gas in the nitriding atmosphere in step (2) comprises ammonia gas.
8. The preparation method according to any one of claims 4 to 7, wherein the microwave reduction in step (3) is carried out by placing the mixed solution in step (3) in a microwave reactor for reaction;
preferably, the power of the microwave reactor is 500-1000W;
preferably, the microwave reduction time in the step (3) is 0.5-5 min;
preferably, the platinum precursor in the step (3) comprises any one or a combination of at least two of chloroplatinic acid, potassium chloroplatinite and platinum acetylacetonate;
preferably, the ruthenium precursor in step (3) comprises any one of ruthenium trichloride, potassium chlororuthenate and ruthenium acetate or a combination of at least two of them.
9. The production method according to any one of claims 4 to 8, characterized by comprising:
(1) mixing a titanium precursor, an organic solvent and an acid solution, and curing for 4-24 hours in a water bath at the temperature of 30-80 ℃ to obtain TiO 2 Gel, mixing the TiO 2 Drying the gel, and calcining at 300-600 ℃ for 2-8 h to obtain TiO 2 A carrier;
(2) the TiO prepared in the step (1) 2 Nitriding the carrier for 1-8 h in the atmosphere of ammonia gas at the nitriding temperature of 600-1200 ℃ to obtain TiN-TiO 2 A carrier;
(3) subjecting the TiN-TiO of the step (2) 2 And mixing the carrier, the platinum precursor, the ruthenium precursor and the ethylene glycol solution, and placing the mixture in a microwave reactor for reaction for 0.5-5 min, wherein the power of the microwave reactor is 500-1000W, so as to obtain the antipole catalyst.
10. A fuel cell characterized in that the anode of the fuel cell comprises therein the anti-reversal catalyst according to any one of claims 1 to 3.
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