CN114335577B - Modified catalyst, membrane electrode, preparation method of modified catalyst and membrane electrode, and fuel cell - Google Patents
Modified catalyst, membrane electrode, preparation method of modified catalyst and membrane electrode, and fuel cell Download PDFInfo
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- CN114335577B CN114335577B CN202111658227.1A CN202111658227A CN114335577B CN 114335577 B CN114335577 B CN 114335577B CN 202111658227 A CN202111658227 A CN 202111658227A CN 114335577 B CN114335577 B CN 114335577B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000002923 metal particle Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000002715 modification method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 22
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- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 17
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000002116 nanohorn Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
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- 239000007787 solid Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 4
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- 229910052742 iron Inorganic materials 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
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- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- 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
Abstract
The invention provides a modified catalyst, a membrane electrode, a preparation method thereof and a fuel cell, belongs to the field of fuel cells, and solves the defect of poor durability of a catalyst or a catalyst layer in the prior art. The modification method of the catalyst comprises the following steps: mixing a catalyst comprising a carrier and metal particles loaded on the carrier and a reducing agent with a first solvent to obtain a mixed solution, carrying out thermal reduction treatment on the mixed solution, and carrying out solid-liquid separation to obtain the modified catalyst.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a modified catalyst, a membrane electrode, a preparation method of the membrane electrode and a fuel cell.
Background
With the increasing environmental protection requirements and the exhaustion of fossil energy, hydrogen energy is increasingly favored by society, and is an ideal clean energy utilization form because no pollution gas is generated and no greenhouse gas is discharged in the utilization process. The fuel cell is a high-efficiency energy conversion device, has the advantages of cleanness, no pollution, high conversion efficiency, high power density and the like, and has become a research focus in the technical field of clean energy utilization. However, the lifetime of fuel cells is a key factor limiting commercial deployment. The latest standards promulgated by the U.S. department of energy (DOE) require that fuel cells have a steady state operating life of over 40000 hours, with a dynamic operating life of no less than 5000 hours.
The fuel cell membrane electrode assembly consists of a gas diffusion layer, a catalyst layer and a proton exchange membrane, and because of the numerous materials involved, and the various operating states of starting/stopping, loading/unloading, dry-wet change (the condition generally has high requirements on the stability of the proton exchange membrane) and the like involved in the operation of the cell, a plurality of possible attenuation mechanisms and complex attenuation processes exist. The fuel cell membrane electrode generally employs a supported catalyst which is composed of a support and a metal supported on the support, and studies have shown that the attenuation of the catalyst in the supported catalyst layer is a major factor affecting the durability of the fuel cell. However, the existing supported catalyst has low stability and poor durability, so that the service life of the membrane electrode is short.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect of poor durability of the catalyst or the catalyst layer in the prior art, thereby providing a modified catalyst, a membrane electrode, a preparation method thereof and a fuel cell.
For this purpose, the invention provides the following technical scheme.
In a first aspect, the present invention provides a method for modifying a catalyst comprising: mixing a carrier, a metal particle catalyst loaded on the carrier and a reducing agent in a first solvent to obtain a mixed solution, carrying out thermal reduction treatment on the mixed solution, and carrying out solid-liquid separation to obtain the modified catalyst.
In one embodiment of the invention, the catalyst and the first solvent are added into a container, the reducing agent is added into the container after the catalyst is dispersed, and the mixture is prepared by stirring. The catalyst is added first for dispersion, so that the reducing agent added later can be reduced uniformly in the initial time.
The catalyst is dispersed in the first solvent by ultrasonic dispersion, the ultrasonic frequency is 20kHz-100kHz, and the ultrasonic duration is 10-30 minutes.
Stirring is carried out after the reducing agent is added, the magnetic stirring speed is 500-1000rpm, and the stirring time is 10-30 minutes.
Further, the mass ratio of the reducing agent to the catalyst is 0.03-0.3; and/or
The concentration of the reducing agent in the mixed solution is 1-10mmol/L.
Further, the carrier is at least one selected from carbon black, porous carbon, carbon fiber, carbon nanotube, carbon nanohorn and graphene; such as BP 2000, VC-72R, GCB, etc.
The metal particles are selected from at least one of platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), and platinum-Me alloy, wherein Me is at least one selected from palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), gallium (Ga), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), silver (Ag), gold (Au), zinc (Zn), tin (Sn), molybdenum (Mo), tungsten (W), lanthanum (La), niobium (Nb), tantalum (Ta), zirconium (Zr), cerium (Ce), yttrium (Y), and rhodium (Rh).
Preferably, the catalyst is Pt/C (platinum/carbon), ptCo/C (platinum cobalt/carbon), ptRu/C (platinum ruthenium/carbon), and illustratively, C in the Pt/C (platinum/carbon), ptCo/C (platinum cobalt/carbon), ptRu/C (platinum ruthenium/carbon) is Vulcan xc72 carbon black.
Further, the modification method satisfies at least one of the conditions a to D:
A. the temperature of the thermal reduction treatment is 160-200 ℃ and the time is 4-10 hours;
B. the solid-liquid separation is centrifugal or filtering, and the solid is dried after the solid-liquid separation, preferably, the drying temperature is 60-100 ℃ and the drying time is 6-10 hours; the drying temperature is too low and the time is too short, the sample is not dried completely, and the first solvent can remain; the drying temperature is too high for too long, so that metal particles can agglomerate to influence the initial activity of the catalyst. Preferably, the centrifugation rate at the time of solid-liquid separation is 5000-10000pm.
C. The first solvent is deionized water or an organic solvent, preferably, the organic solvent is methanol or DMF;
D. the reducing agent is at least one selected from potassium borohydride, sodium borohydride, citric acid and ethylene glycol.
In a second aspect, the present invention provides a modified catalyst, prepared by the above-described method of modifying a catalyst.
Further, the surface oxygen content of the carrier is 4-7at.%, and/or the particle size of the metal particles is 3.3-4.2 nm.
In a third aspect, the present invention provides a catalyst layer comprising the modified catalyst described above and a perfluorosulfonic acid resin.
In a fourth aspect, the present invention provides a membrane electrode comprising a gas diffusion layer, the catalyst layer described above and a proton exchange membrane.
In a fifth aspect, the present invention provides a method for preparing a membrane electrode, comprising: and mixing the modified catalyst and perfluorinated sulfonic acid resin in a second solvent to prepare slurry, uniformly coating the slurry on the cathode side of the proton exchange membrane, aligning gas diffusion layers on two sides of the proton exchange membrane, and hot-pressing to prepare the membrane electrode.
By way of example, the perfluorosulfonic acid resin may be selected from D520, D2020, D1020, etc. available from DuPont company (supplier: shanghai electric Co., ltd.).
Further, at least one of the conditions (1) to (8):
(1) The mass ratio of the modified catalyst to the perfluorinated sulfonic acid resin is (6-8): (2-40), preferably 7:3. the perfluorinated sulfonic acid resin can transmit protons, has good hydrophilicity, and is not conductive; the ratio should be at a suitable value, taking into account the conductivity of the catalytic layer in combination, adjusting the hydrophilicity and hydrophobicity to optimize water management, and three-phase interface optimization.
(2) The mass ratio of the second solvent to the modified catalyst is (1000-200): 1. too large proportion, too thin dispersion, too long time for solvent evaporation in the spraying process; the proportion is too small, the dispersion liquid is too thick, and agglomeration is easy to occur after ultrasonic dispersion.
(3) Dispersing the modified catalyst and the perfluorinated sulfonic acid resin in a second solvent by adopting ultrasonic, wherein the ultrasonic frequency is 20kHz-100kHz, the ultrasonic time is 30-120 min, and the ultrasonic temperature is controlled to be 15-30 ℃; too high a temperature can cause poor slurry dispersion;
(4) Uniformly coating the slurry on the cathode side of the proton exchange membrane by adopting ultrasonic spraying;
(5) Slurry prepared by coating modified catalyst or slurry prepared by coating unmodified catalyst on the anode side of the proton exchange membrane; the cathode of the fuel cell has a harsher environment, the catalyst layer of the cathode adopts the catalyst modified by the invention, and the anode can well reduce the decay rate of the membrane electrode and prolong the service life of the membrane electrode even if adopting the existing commercial catalyst.
(6) The loading amount of the slurry coated on the two sides of the proton exchange membrane enables the loading amount of the metal particles to be anode: 0.05-0.2mg Pt cm -2 Cathode: 0.3-0.8mg Pt cm -2 ；
(7) The second solvent is at least one of methanol, isopropanol and deionized water;
(8) The hot pressing temperature is 110-140 ℃, the hot pressing pressure is 0.2-2MPa, and the hot pressing time is 1-2min.
In a sixth aspect, the present invention provides a fuel cell comprising the membrane electrode or the membrane electrode prepared by the above-described preparation method.
The fuel cell is used in a vehicle or a power station.
The attenuation mechanisms of platinum-based catalysts are mainly two types: 1) Agglomeration, growth and dissolution loss of platinum nano particles, which results in reduced electrochemical activity specific surface; 2) The carbon carrier is oxidized and corroded, so that platinum nano particles fall off, and the active site is totally invalid. When the surface of the platinum nanoparticle has more defect sites, the platinum nanoparticle is easy to age according to the principle of lowest surface energy, and meanwhile, under the high potential and oxygen-enriched environment of a cathode of a fuel cell, the platinum atoms of the small particles with more unstable defects are more easy to migrate, run off or grow on the large particles, so that effective active sites are reduced, and the electrochemical active area is reduced (Ostwald aging). The carbon material carrier is in an amorphous state, the surface of the carbon material carrier is rich in various oxygen-containing groups, and the oxygen-containing groups are easy to oxidize to generate carbon dioxide under the cathode environment of the fuel cell, so that the capability of fixing platinum nano particles is reduced. Therefore, the defect sites on the platinum surface and the oxygen content on the carbon material surface need to be controlled within a reasonable range.
The technical scheme of the invention has the following advantages:
1. the modification method of the catalyst provided by the invention comprises the following steps: and mixing the catalyst and the reducing agent in a first solvent to obtain a mixed solution, and performing thermal reduction treatment on the mixed solution to obtain the modified catalyst. The invention carries out one-step simple thermal reduction treatment on the catalyst (the existing commercial catalyst), firstly, the high temperature leads the metal particles to have surface reconstruction, the defect sites are reduced, and the invention is beneficial to improving the stability of oxygen reduction catalysis. And secondly, under the treatment of the reducing agent, the content of the carrier oxygen-containing groups in the non-supported area can be reduced, so that the purpose of improving the durability of the catalyst is achieved, and the electrochemical stability of the modified catalyst is improved. The preparation method is simple and easy to implement, has strong operability, and can realize the large-scale preparation of the catalyst.
2. According to the modification method of the catalyst, the mass ratio of the reducing agent to the catalyst is 0.03-0.3, the reducing agent is mainly used for modifying the carbon carrier, the reduction of the oxygen content of the carbon carrier is facilitated, the oxygen content is regulated to a proper value, and the stability of the carbon carrier is improved, and meanwhile, enough oxygen functional group rivet platinum particles are provided to ensure the initial catalytic activity.
The concentration of the reducing agent in the mixed solution is 1-10mmol/L, the reducing rate and the reducing degree are controlled by the concentration of the reducing agent, and the reducing agent is regulated to a moderate value, so that the modification of the carbon carrier and the platinum particles are not separated.
3. The oxygen content of the surface of the carrier is 4-7at%, the oxygen content of the surface of the carrier is reduced by 20% -30% compared with the oxygen content of the surface of the existing commercial catalyst, the defect site number of metal particles is obviously reduced, the particle size of the metal particles is slightly increased compared with that of untreated commercial platinum-based catalyst, the shape of the metal particles is more regular, and the edges of the nano particles are flatter. Thereby greatly improving the electrochemical stability of the catalyst, effectively and obviously improving the durability of the membrane electrode, and further improving the durability of the membrane electrode of the fuel cell.
4. The membrane electrode provided by the invention comprises a gas diffusion layer, a catalyst layer and a proton exchange membrane, wherein the catalyst layer comprises the catalyst or the catalyst prepared by the preparation method. The attenuation of the catalyst in the catalytic layer is a main factor affecting the durability of the fuel cell, and the membrane electrode provided by the invention adopts the catalyst with high durability, so that the prepared membrane electrode and the fuel cell have good durability. The membrane electrode prepared by the method runs for 100 hours under a dynamic working condition, and the voltage decay rate is 60 mu V/h and is lower than 72.5 mu V/h reported in the literature.
5. According to the preparation method of the membrane electrode, the slurry is uniformly coated on the proton exchange membrane by adopting ultrasonic spraying, and the ultrasonic spraying is beneficial to reducing the contact resistance of the membrane electrode and improving the performance of the membrane electrode.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a transmission electron microscope image of Pt/C-1 prepared in example 1;
FIG. 2 is a high angle annular dark field scanning transmission electron micrograph of a commercial Pt/C (a, b) used in example 1 and Pt/C-1 (C, d) prepared in example 1;
FIG. 3 is a polarization curve obtained by catalyst oxygen reduction performance test for Pt/C-1 prepared in example 1 and commercial Pt/C used in example 1;
FIG. 4 is a graph showing the change in electrochemical activity area of Pt/C-1 prepared in example 1 and commercial Pt/C used in example 1 before and after 10000 cycles of potential cycling scan obtained by catalyst stability test;
FIG. 5 is a graph showing the voltage change of the membrane electrode MEA-1 prepared in example 1 under 100h variable load operating conditions;
FIG. 6 is a graph showing the polarization curves of the membrane electrode MEA-1 prepared in example 1 before and after 100h variable load operation;
FIG. 7 is a polarization curve of example 2Pt/C-2 and commercial Pt/C used in example 1;
FIG. 8 is a graph showing the change in electrochemically active area of Pt/C-2 of example 2 and commercial Pt/C used in example 1 before and after 10000 cycles of potential cycling scan;
FIG. 9 is a transmission electron microscope image of a commercial Pt/C used in example 1.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
50mg of a commercial Pt/C catalyst (JM (Johnson Matthey, zhuang Xin) 60% Pt/C) was added to the kettle liner of polytetrafluoroethylene, and the mixture was sonicated in 50mL of deionized water at 50kHz for 10 minutes; adding 6.4mg of potassium borohydride into the dispersion liquid, stirring at the stirring speed of 500rpm for 30min; then the obtained reaction kettle filled with the mixed solution is placed in an oven to be continuously aged for 6 hours at the reaction temperature of 180 ℃, cooled to room temperature, centrifugally collected at 10000rpm, and dried at 80 ℃ for 6 hours to obtain the high-stability platinum-carbon catalyst which is marked as Pt/C-1.
Through X-ray photoelectron spectroscopy (XPS) analysis, the oxygen content of the surface of the carbon carrier of Pt/C-1 is 5.71 at%; the average particle diameter of the platinum particles was 3.40nm. The Pt/C-1 platinum particles had few defects and a regular morphology, as shown in FIG. 1, and a significant reduction in defects was observed by high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) in this example compared to commercial Pt/C, as shown in FIG. 2.
36mg of a Pt/C-1 catalyst and perfluorosulfonic acid resin (DuPont, D520) (the mass ratio of the Pt/C-2 catalyst to the perfluorosulfonic acid resin is 7:3) are ultrasonically dispersed into 30mL of isopropanol solution to prepare slurry, wherein the ultrasonic frequency is 50kHz, the ultrasonic time is 30min, and the temperature is 20 ℃. Spraying the slurry on the proton exchange membrane by adopting an ultrasonic spraying method(Dupont, nafion 212) on the cathode side, and then a commercial platinum carbon catalyst was sprayed on the anode side in the same manner to give a cathode loading of 0.6mg Pt cm -2 The anode loading was set to 0.2mg Pt cm -2 Finally, gas diffusion layers (Sigracet, 22 BBB) were aligned on both sides, and hot-pressed at 125℃and a pressure of 0.20MPa for 2 minutes to obtain a high-stability membrane electrode, which was designated as MEA-1.
Example 2
The modification method of the catalyst in example 2 was substantially the same as in example 1 except that the mass of potassium borohydride was changed to 3.2mg to obtain a highly stable platinum carbon catalyst, which was designated as Pt/C-2.
The surface oxygen content of the Pt/C-2 carbon support was 6.90at.% and the average particle size of the platinum particles was 3.30nm as analyzed by X-ray photoelectron spectroscopy (XPS).
Example 3
50mg of commercial PtCo/C catalyst is added into a polytetrafluoroethylene reaction kettle liner, and is dispersed in 50ml of methanol by ultrasonic wave with the ultrasonic frequency of 100KHz for 10 minutes; adding 15mg of citric acid into the dispersion, stirring at 500rpm for 30min; then the obtained reaction kettle filled with the mixed solution is placed in an oven to be continuously aged for 10 hours at the reaction temperature of 160 ℃, then cooled to room temperature, and then centrifugally collected at 5000rpm, and dried at 100 ℃ for 6 hours to obtain the PtCo/C catalyst with high stability, which is marked as PtCo/C-3.
Then 30mg of PtCo/C-3 obtained above and perfluorosulfonic acid resin (the mass ratio of PtCo/C-5 catalyst to perfluorosulfonic acid resin is 6:40) are ultrasonically dispersed into 30ml of methanol solution to prepare slurry, the ultrasonic frequency is 100kHz, the ultrasonic time is 30min, and the ultrasonic temperature is controlled at 30 ℃. The slurry is sprayed on the cathode side of the proton exchange membrane by adopting an ultrasonic spraying method, and then a commercial platinum carbon catalyst is sprayed on the anode side by adopting the same method, wherein the loading amount is that of the anode: 0.05mg Pt cm -2 Cathode: 0.3mg Pt cm -2 And finally, aligning the gas diffusion layers on two sides, and hot-pressing for 1 minute at 110 ℃ and 2MPa to obtain the high-stability membrane electrode.
Example 4
50mg of commercial PtRu/C catalyst is added into a polytetrafluoroethylene reaction kettle liner, and is dispersed in 50ml of DMF by ultrasound with the frequency of 20KHz for 30 minutes; 10mg of potassium borohydride was added to the above dispersion, followed by stirring at a stirring rate of 1000rpm for 10 minutes; then the obtained reaction kettle filled with the mixed solution is placed in an oven to be continuously aged for 4 hours at the reaction temperature of 200 ℃, then cooled to room temperature, and then centrifugally collected at 8000rpm, and dried at 60 ℃ for 10 hours to obtain the PtRu/C catalyst with high stability, which is marked as PtRu/C-4.
Then 30mg of PtRu/C-4 obtained above and perfluorinated sulfonic acid resin (the mass ratio of PtRu/C-6 catalyst to perfluorinated sulfonic acid resin is 8:2) are ultrasonically dispersed into 30ml of deionized water to prepare slurry, the ultrasonic frequency is 20kHz, the ultrasonic time is 120min, and the ultrasonic temperature is controlled at 15 ℃. The slurry is sprayed on the cathode side of the proton exchange membrane by adopting an ultrasonic spraying method, and then a commercial platinum carbon catalyst is sprayed on the anode side by adopting the same method, wherein the loading amount is that of the anode: 0.15mg Pt cm -2 Cathode: 0.5mg Pt cm -2 And finally, aligning the gas diffusion layers on two sides, and hot-pressing for 1.5 minutes at 140 ℃ and 2MPa to obtain the high-stability membrane electrode.
Comparative example 1
This comparative example also provides a method of preparing a membrane electrode having substantially the same process parameters as example 1, except that the modified catalyst Pt/C-1 of example 1 was replaced with the commercial Pt/C catalyst (JM 60% Pt/C) of example.
The surface oxygen content of the commercial Pt/C carbon support was 7.69at.%, the number of defects on the platinum particles was large and the morphology was irregular, as shown in fig. 9. The average particle diameter of the platinum particles was 2.83nm.
Test example 1
The following tests were performed on the catalyst and membrane electrode:
catalyst oxygen reduction performance test: saturated with 0.1M HClO in nitrogen 4 In the range of 0 to 1.2V vs RHE and 100mV s -1 Activated for 20 turns at the sweep rate of (2) and then at O 2 Saturated 0.1M HClO 4 The potential range of the test voltage-current relation curve in the electrolyte is 0-1.2V vs RHE, the scanning direction is negative scanning, and the scanning speed is 5mV s -1 The working electrode rotation speed is 1600rmp, and the current obtained by the test is subtracted by N 2 And (3) saturating electric double layer charging current in the electrolyte to obtain a polarization curve of the catalyst, and comparing the oxygen reduction performance of the catalyst through half-wave potential.
Catalyst stability test: the cyclic voltammetry is adopted, the scanning voltage interval is controlled to be 0.6-1.1V, and the scanning speed is controlled to be 50mV s -1 The number of the scanning turns is 10000, and the electrochemical activity area (recorded as 10000 turns) is tested after 10000 turns and compared with the electrochemical activity area (recorded as initial) before the circulation.
Membrane electrode polarization curve test: operating temperature 80 ℃, relative humidity 100% RH, back pressure 1bar, anode hydrogen flow 500mL min -1 Cathode air flow 1600mL min -1 The current density is from 0A cm -2 Pulling up with a step length of 100mA cm -2 Each step was stable for 5min and the pull-up stopped when the voltage was below 0.3V.
Membrane electrode stability test: according to the test condition of the polarization curve, when the current density is pulled up by 500mA cm -2 Stably operating for 2 hours, and then pulling up to 1A cm -2 Stabilizing for 2h, and then reducing the current by 500mAcm -2 The reaction was allowed to stand for 2 hours and cycled 25 times according to the procedure for a total of 100 hours. And then carrying out a polarization curve test to obtain a polarization curve after 100h, and comparing the polarization curve with an initial polarization curve before 100h stability test is not carried out.
The experimental process must not be disturbed by the outside to avoid break points. The results are shown in FIGS. 1-8 and the tables below.
TABLE 1 Properties of Pt/C-1, pt/C-2 and commercial Pt/C
As can be seen from FIGS. 3 and 7, the half-wave potential (E 1/2 ) Is 0.909V, 20mV higher than the half-wave potential of the original unmodified commercial Pt/C, the half-wave potential of Pt/C-2 (E 1/2 ) The half-wave potential of the catalyst is improved by 11mV compared with that of the original unmodified commercial Pt/C at 0.900V, which shows that the oxygen reducibility of the modified catalyst is improved compared with that of the commercial Pt/C.
As shown in fig. 4 and 8, after 10000 cycles of potential cycling acceleration durability test, the electrochemical active area of Pt/C-1 is only lost by 32.84%, the electrochemical active area of Pt/C-2 is only lost by 33.21%, and the electrochemical active area loss is lower than that of original unmodified commercial Pt/C (about 45.04%), so that the stability of the modified catalyst is improved.
MEA-1 at 1Acm -2 At a current density, the voltage reached 0.64V, FIG. 5 was at 500mAcm -2 And 1Acm -2 The current density is changed and run for 100 hours, the voltage decay rate is 60 mu V/h through testing the polarization curve, and particularly as shown in figure 6, the voltage decay rate of the membrane electrode is lower, and the membrane electrode has better stability.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (17)
1. A method for modifying a catalyst, comprising: mixing a catalyst comprising a carrier and metal particles loaded on the carrier with a reducing agent in a first solvent to obtain a mixed solution, carrying out thermal reduction treatment on the mixed solution, and carrying out solid-liquid separation to obtain a modified catalyst;
the carrier is at least one of carbon black, porous carbon, carbon fiber, carbon nanotube, carbon nanohorn and graphene;
the mass ratio of the reducing agent to the catalyst is 0.03-0.3;
the temperature of the thermal reduction treatment is 160-200 o C, the time is 4-10 hours.
2. The method for modifying a catalyst according to claim 1, wherein the concentration of the reducing agent in the mixed solution is 1 to 10mmol/L.
3. The method for modifying a catalyst according to claim 1 or 2, wherein the metal particles are at least one metal element selected from the group consisting of platinum, palladium, ruthenium, iridium, osmium and platinum-Me alloy, wherein Me is at least one metal element selected from the group consisting of palladium, ruthenium, iridium, osmium, gallium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, gold, zinc, tin, molybdenum, tungsten, lanthanum, niobium, tantalum, zirconium, cerium, yttrium and rhodium.
4. The method for modifying a catalyst according to claim 1 or 2, wherein the catalyst is Pt/C, ptCo/C, ptRu/C.
5. The modification method of a catalyst according to claim 1 or 2, wherein the modification method satisfies at least one of the conditions a to C:
A. the solid-liquid separation is centrifugal or filtering, and the solid is dried after the solid-liquid separation;
B. the first solvent is water or an organic solvent;
C. the reducing agent is at least one selected from potassium borohydride, sodium borohydride, citric acid and ethylene glycol.
6. The method for modifying a catalyst according to claim 5, wherein the drying temperature is 60 to 100 o And C, drying for 6-10 hours.
7. The method for modifying a catalyst according to claim 5, wherein the organic solvent is methanol or DMF.
8. A modified catalyst obtainable by a modification process of the catalyst of any one of claims 1 to 7.
9. The modified catalyst according to claim 8, wherein the oxygen content of the surface of the carrier of the modified catalyst is 4-7at.% and/or the particle size of the metal particles of the modified catalyst is 3.3-4.2 nm.
10. A catalyst layer comprising the modified catalyst according to claim 8 or 9 and a perfluorosulfonic acid resin.
11. A membrane electrode comprising the catalyst layer of claim 10, further comprising a gas diffusion layer and a proton exchange membrane.
12. A method of preparing the membrane electrode of claim 11, comprising: and mixing the modified catalyst and perfluorinated sulfonic acid resin in a second solvent to prepare slurry, uniformly coating the slurry on the cathode side of the proton exchange membrane, and hot-pressing gas diffusion layers on two sides of the proton exchange membrane to prepare the membrane electrode.
13. The method for producing a membrane electrode according to claim 12, wherein at least one of the conditions (1) to (8) is satisfied:
(1) The mass ratio of the modified catalyst to the perfluorinated sulfonic acid resin is (6-8): (2-40);
(2) The mass ratio of the second solvent to the modified catalyst is (1000-200): 1, a step of;
(3) The modified catalyst and the perfluorinated sulfonic acid resin are dispersed in a second solvent by adopting ultrasonic, the ultrasonic frequency is 20kHz-100kHz, the ultrasonic time is 30-120 min, and the ultrasonic temperature is controlled to be 15-30 o C；
(4) Coating the slurry on the cathode side of the proton exchange membrane by adopting ultrasonic spraying;
(5) Coating the slurry of claim 8 or coating unmodified catalyst on the anode side of the proton exchange membrane;
(6) Cathode loading of metal particles: 0.3-0.8mg Pt cm -2 ；
(7) The second solvent is at least one of methanol, isopropanol and water;
(8) The hot pressing temperature is 110-140 ℃, and the hot pressing pressure is 0.2-2MPa.
14. The method for producing a membrane electrode according to claim 13, wherein the mass ratio of the modified catalyst to the perfluorosulfonic acid resin is 7:3.
15. the method for producing a membrane electrode according to claim 13, wherein the anode supporting amount of the metal particles: 0.05-0.2. 0.2mg Pt cm -2 。
16. The method for producing a membrane electrode according to claim 13, wherein the hot pressing time is 1 to 2 minutes.
17. A fuel cell comprising the membrane electrode of claim 11 or the membrane electrode prepared by the method of preparing a membrane electrode of any one of claims 12-16.
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