CN114388827A - Batch preparation method of catalyst for fuel cell - Google Patents
Batch preparation method of catalyst for fuel cell Download PDFInfo
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- CN114388827A CN114388827A CN202111547596.3A CN202111547596A CN114388827A CN 114388827 A CN114388827 A CN 114388827A CN 202111547596 A CN202111547596 A CN 202111547596A CN 114388827 A CN114388827 A CN 114388827A
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Classifications
-
- 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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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 relates to a batch preparation method of a catalyst for fuel cells, which comprises the following steps: mixing a carrier, formic acid and ethylene glycol, heating and reacting with water, a chloroplatinic acid solution and a sodium carbonate solution in an inert gas atmosphere, and carrying out aftertreatment on the obtained reaction product mixed solution to obtain the carbon-supported nano platinum particle catalyst. Compared with the prior art, the fuel cell catalyst prepared by the invention has moderate particle size, uniform precious metal loading, common raw and auxiliary materials, no pressure and high temperature in the reaction process, no surfactant or coating agent, and the precious metal loading capacity of the prepared catalyst can be adjusted according to the proportion of different raw materials; meanwhile, the mass production scale of the prepared catalyst can be adjusted according to the dosage of different raw materials and needs, which is beneficial to greatly promoting the scale process of the domestic catalyst.
Description
Technical Field
The invention belongs to the technical field of fuel cell catalysts, and relates to a batch preparation method of a fuel cell catalyst.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have great advantages in the application of power sources for vehicles, such as high energy conversion efficiency, rapid start-up, low temperature operation, zero emission, etc., and are known as a potential energy substitute for conventional fossil fuels. In PEMFCs, Hydrogen Oxidation Reaction (HOR) occurring at the anode and Oxygen Reduction Reaction (ORR) occurring at the cathode are thermodynamically feasible, but do not occur under general conditions due to their poor chemical kinetic properties. In this case, it is necessary to introduce catalysts for these two reactions, and to reduce the activation energy thereof, so that the electrode reaction can proceed spontaneously in a large amount, thereby improving the energy conversion efficiency of the fuel cell. Based on better catalytic activity and stability, PEMFC cathode catalysts generally employ high-loading and uniformly dispersed Pt/C.
Generally, as an electrochemical catalyst of PEMFC, the following 4-point requirements are satisfied first:
(1) a higher catalytic activity is desired. That is, the reduction degree of the activation energy of the electrode reaction is appropriate, and the activation loss of the electrode reaction can be reduced by suppressing the occurrence of the side reaction of the electrode while the target reaction is realized. For example, the 4 electron reaction potential of the fuel cell electrode is high, the current efficiency is high, and the degradation influence of substances such as hydrogen peroxide generated by the 2 electron reaction on the proton exchange membrane and the ionomer can be avoided.
(2) Sufficient durability is required. Namely, when the fuel cell carries out electrochemical reaction, agglomeration, dissolution, inactivation and the like which influence the catalytic reaction of the fuel cell are not or as little as possible, so that the long service life and the functional stability of the fuel cell are ensured.
(3) A sufficiently high porosity is required. Namely, when the electrode reaction is carried out, a good gas and water transmission channel can be ensured, and the mass transfer loss of the electrode reaction is reduced.
(4) Good electrical conductivity is required. That is, conduction of electrons in the electrode is ensured, and a carrier having good conductivity is generally used to obtain high conductivity, thereby reducing ohmic loss of electrode reaction.
The catalyst of the present invention can promote the electrochemical reaction inside fuel cell. During the operation of the fuel cell, the transfer of two-phase flow of reactant gas and product water, gas and liquid, is carried out, accompanied by the transfer of protons and electrons. The catalyst particles and ionic polymer (Nafion is generally used) are mixed and dispersed by a solvent to form slurry, and the slurry is sprayed, slit coated or transferred to prepare catalyst layers of the fuel cell on two sides of a proton exchange membrane. Only those platinum particles that are capable of contacting the reactant gases and have associated proton-electron transport channels are catalytic. The location where the reactant gas, Pt particles and ionomer are combined is generally referred to as the three-phase reaction interface, which is essentially the junction of the electron, proton and molecular (reactant gas) transport channels. The more reactive sites in the catalytic layer, the stronger the activity of each catalytic site, the faster the catalytic reaction speed and the higher the efficiency.
Most of the current catalyst preparations have a number of problems: the preparation process of the catalyst is complicated, and the control conditions are severe, so that the batch manufacturing process is limited, such as high-temperature and high-pressure experimental conditions; coating agents and the like used in the preparation process are difficult to remove, so that the adsorption of reaction gas and the effective transmission of electrons between the catalyst and the carrier are limited; too long reaction time, etc. These problems affect the performance of the catalyst or limit the mass production of the catalyst, which is an obstacle to the large-scale commercial development of fuel cells.
Chinese patent application CN109216716A discloses a preparation method of a Pt/C catalyst for a fuel cell with high Pt loading capacity, belonging to the field of new energy materials. The invention of CN109216716A provides a preparation method of a Pt/C catalyst for a fuel cell with high Pt loading, which comprises the following steps: putting the carbon powder subjected to presintering at 1600-2600 ℃ into a platinum-containing solution, adding sodium carbonate and formic acid, carrying out reduction reaction in a water bath at 60-90 ℃, and drying at 80-100 ℃ to obtain the catalyst. The invention has the beneficial effects that: (1) the heating mode is water bath, the method is suitable for a larger reaction vessel, and the whole preparation process can realize the mass and repeatable production of the high-load Pt/C catalyst; (2) the active component is loaded on the carrier by a liquid phase reduction method, and the preparation process is simple and convenient; (3) the carbon powder is sintered at high temperature, and the obtained catalyst has good activity and stability. However, the CN109216716A patent uses a high temperature treatment (1600-The defect sites on the surface of the carrier are correspondingly reduced, and a higher electrochemical active area (ECSA about 45-47 m) is difficult to obtain when active metal nanoparticles are deposited2g-1) The utilization rate of noble metal platinum is reduced; meanwhile, the activity of the catalyst is not high as shown by the results of a linear voltammetry (LSV) test. The ECSA of the invention reaches 67.87m2g-1Over about 50% of CN109216716A, the mass activity of LSV at 0.9V also reached 95.14mA mg-1. And the carbon carrier of CN109216716A needs high-temperature graphitization treatment, so that the time and energy consumption cost is large. For pretreatment, the invention also provides a carbon acid-washing etching scheme, which is more favorable for the attachment of metal particles on the surface of the carrier. The minimum number of catalyst washes and the final conductivity criteria are also well defined. The catalyst drying part also adopts a sectional drying process, water is remained on the surface of the catalyst during the primary low-temperature drying stage, and gap water between catalyst particles is mainly dried during the secondary high-temperature drying stage, so that the catalyst can be prevented from agglomerating at a high temperature for a long time, and energy is saved. In addition, the treatment process of the invention uses conventional medicines at normal temperature and normal pressure, does not need to use a surfactant or a coating agent, and can adjust the noble metal loading capacity of the prepared catalyst according to the proportion of different raw materials; meanwhile, the mass production scale of the prepared catalyst can be adjusted according to the consumption of different raw materials and needs, the technical barrier of batch preparation of the fuel cell catalyst is broken through, and the scale process of the domestic catalyst can be greatly promoted.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a method for preparing a catalyst for fuel cells in a batch manner.
The purpose of the invention can be realized by the following technical scheme:
a batch preparation method of a catalyst for a fuel cell, comprising:
mixing a carrier, formic acid and ethylene glycol, heating and reacting with water, a chloroplatinic acid solution and a sodium carbonate solution in an inert gas atmosphere, and carrying out aftertreatment on the obtained reaction product mixed solution to obtain the carbon-supported nano platinum particle catalyst.
Further, the carrier comprises at least one of carbon nanospheres, carbon nanoclusters, carbon nanotubes, graphene, mesoporous carbon, macroporous carbon, graphitized carbon, nitrogen-doped carbon material, boron-doped carbon material, sulfur-doped carbon material, silicon carbide, titanium dioxide, tungsten oxide and zinc oxide.
Further, when the carrier is a carbon material, in the step 1), the carrier is pretreated and then mixed with formic acid and ethylene glycol, wherein the pretreatment method comprises the following steps:
and mixing the carbon material with ethanol and sulfuric acid solution, and sequentially heating, stirring, settling, washing and drying to obtain the pretreated carrier.
Further, the concentration of the sulfuric acid solution is 5-30 wt%, the mass ratio of the carbon material to the sulfuric acid solution is (1-5) to 20, and the mass ratio of the ethanol to the sulfuric acid solution is 1 (5-10);
in the heating and stirring process, the stirring temperature is 60-80 ℃, and the stirring time is 1-3 h;
in the drying process, the drying temperature is 160-.
As a preferred technical scheme, the mixing process of the carrier, the formic acid and the ethylene glycol comprises ultrasonic dispersion, wherein the ultrasonic frequency is 5-50kHz, the ultrasonic power is 500-800W, and the ultrasonic time is 3-30 min.
Furthermore, the concentration of the chloroplatinic acid solution is 25-75 wt%, the mass ratio of the chloroplatinic acid to the formic acid is (0.8-1.2):1, the mass ratio of platinum in the chloroplatinic acid to the carbon material is 1 (0.56-3.57), the mass ratio of ethylene glycol to water is (3-6):1, and the mass ratio of water to the formic acid is (4-5): 1.
Furthermore, the mass ratio of sodium carbonate to water in the sodium carbonate solution is (5-8):20, and the mass ratio of the sodium carbonate solution to formic acid is (30-50): 1.
As a preferred technical scheme, the temperature is raised to 60-90 ℃ before the sodium carbonate solution is added, so as to avoid undissolved sodium carbonate particles in the reaction process.
Further, in the heating reaction process, the reaction temperature is 60-90 ℃, the reaction time is 3-6h, the reaction atmosphere is a continuously flowing nitrogen atmosphere, the nitrogen flow rate is 1.5-2.0L/min, and the stirring rotation speed is 200-300 rpm.
Further, the post-processing process comprises: and mixing the reaction product mixed solution with an acid solution, standing and settling, and sequentially washing, filtering and drying the sediment to obtain the carbon-supported nano platinum particle catalyst.
Further, the acid solution is 20-30 wt% dilute sulfuric acid solution, and after the reaction product mixed solution is mixed with the acid solution, the pH value is adjusted to 3-5;
after multiple water washing, the conductivity of the supernatant is not more than 5 muS-cm-1。
Further, the drying process comprises: placing the filter residue in an inert gas atmosphere with the flow rate of 0.6-0.8L/min, and heating and drying for 0.5-1h at the temperature of 110-; and then vacuum drying is carried out for 2-4h at the temperature of 180 ℃ and 200 ℃, thus obtaining the carbon-supported nano platinum particle catalyst.
Compared with the prior art, the invention has the following characteristics:
1) the invention is based on a fuel cell catalyst which is easy to realize, realizes the catalyst with proper particle size, uniform noble metal load and wide load range distribution, the raw and auxiliary materials are common medicines, the reaction process has no pressure and high temperature, a surfactant or a cladding agent is not needed, and the noble metal load capacity of the prepared catalyst can be adjusted according to the proportion of different raw materials; meanwhile, the mass production scale of the prepared catalyst can be adjusted according to the consumption of different raw materials and needs, the technical barrier of batch preparation of the fuel cell catalyst is broken through, and the scale process of the domestic catalyst can be greatly promoted;
2) the method has the advantages of simple required equipment and mature process, can greatly reduce the condition requirements of the preparation process compared with most of the existing preparation processes, and can obviously improve the preparation efficiency and the localization level of the catalyst;
3) the preparation method has high repeatability of the preparation process, the consistency of the catalysts in different batches is kept well, the amount of reaction substances can be amplified in equal proportion according to the mass production scale of the catalysts, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 is a CV curve of the carbon-supported nano platinum particle catalyst prepared in example 1;
FIG. 2 is a LSV curve of the carbon-supported nano platinum particle catalyst prepared in example 1;
FIG. 3 is a scanning electron microscope image of the carbon-supported nano platinum particle catalyst prepared in example 1;
fig. 4 is a distribution diagram of the particle size of the carbon-supported nano platinum particle catalyst prepared in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A batch preparation method of a catalyst for a fuel cell, comprising:
s1: weighing and mixing the carrier, ethanol and sulfuric acid solution, heating and stirring, standing and settling, pouring out supernatant, washing sediment with deionized water, repeating the processes of settling and washing until the supernatant is neutral, filtering, drying and crushing to obtain a pretreated carrier, and sealing and storing for later use;
the carrier comprises carbon nano materials such as carbon nanospheres, carbon nano branches, carbon nano tubes, graphene, mesoporous carbon, macroporous carbon, graphitized carbon and the like, or modified carbon materials such as nitrogen-doped carbon materials, boron-doped carbon materials, sulfur-doped carbon materials and the like, or at least one of non-carbon materials such as silicon carbide, titanium dioxide, tungsten oxide, zinc oxide and the like;
the concentration of the sulfuric acid solution is 5-30 wt%, the mass ratio of the carrier to the sulfuric acid solution is (1-5) to 20, and the mass ratio of the ethanol to the sulfuric acid solution is 1 (5-10); in the heating and stirring process, the stirring temperature is 60-80 ℃, and the stirring time is 1-3 h; in the drying process, the drying temperature is 160-;
s2: stirring and mixing the pretreatment carrier, formic acid and glycol in a water bath environment at 0-20 ℃, ultrasonically dispersing for 3-30min at the ultrasonic frequency of 5-50kHz and the ultrasonic power of 500-800W, and adding into a reaction kettle;
then adding chloroplatinic acid aqueous solution, glycol and water, stirring for 10-40min at the rotation speed of 200-300rpm at the temperature of 60-90 ℃ in the nitrogen atmosphere with the flow rate of 0.6-2.0L/min, removing air in the reaction kettle and uniformly mixing the materials;
wherein, the concentration of the chloroplatinic acid aqueous solution is 25-75 wt%, the mass ratio of the chloroplatinic acid to the formic acid is (0.8-1.2):1, the mass ratio of platinum to the carbon material in the chloroplatinic acid is 1 (0.56-3.57) according to the platinum loading capacity of the prepared catalyst (10-60%), the mass ratio of the total using amount of the glycol to the water is (3-6):1, and the mass ratio of the water to the formic acid is (4-5): 1;
s3: adding a sodium carbonate aqueous solution into the reaction kettle, and stirring and reacting for 3-6h at the rotating speed of 200-300rpm at the temperature of 60-90 ℃ in a nitrogen atmosphere with the flow rate of 1.5-2.0L/min to obtain a reaction product mixed solution;
wherein the mass ratio of sodium carbonate to water in the sodium carbonate solution is (5-8) to 20, and the mass ratio of the sodium carbonate solution to formic acid is (30-50) to 1;
s4: mixing the reaction product mixed solution with 20-30 wt% dilute sulfuric acid solution until the pH of the solution is 3-5, adding water, stirring, standing at room temperature for settling, pouring out the supernatant, and repeating the processes of adding water, stirring and standing for settling until the conductivity of the supernatant is not more than 5 mu S cm-1；
Filtering, taking filter residue, placing in an inert gas atmosphere with the flow rate of 0.6-0.8L/min, and heating and drying at the temperature of 110-; and then vacuum drying is carried out for 2-4h at the temperature of 180 ℃ and 200 ℃, thus obtaining the carbon-supported nano platinum particle catalyst.
Preferably, step S4 can be repeated multiple times to obtain a carbon-supported nano platinum particle catalyst with higher purity.
Preferably, the dilute sulfuric acid solution is added with slow stirring to prevent splashing of the liquid due to vigorous reaction.
Preferably, in the process of adding water and stirring, the primary water adding amount is more than 5 times of the volume of the reaction product mixture; the repetition times of the processes of adding water, stirring and standing for settling are not less than 8.
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the carbon carriers (carbon powders) used were those obtained from Cabot corporation, U.S.A., Vulcan XC-72R, chloroplatinic acid, etc., which were obtained from Chemicals, Inc., national drug group and were of analytical grade (AR) and were not further processed. Meanwhile, tests such as Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) are conventional detection means in the field and are used for characterizing the electrochemical performance of the catalyst. A Transmission Electron Microscope (TEM) is used to observe the surface morphology of the catalyst and to count the particle size of the supported metal particles.
Example 1:
a batch preparation method of a catalyst for a fuel cell, comprising the steps of:
1) weighing 100g of unwashed carbon powder on an analytical balance by using a beaker, simultaneously adding 200g of ethanol and 1000g of 10 wt% sulfuric acid aqueous solution on an electronic balance, then putting the beaker into a water bath at 70 ℃, heating and stirring for 2h, standing and settling, pouring out supernate, adding deionized water to continue settling, repeating the cleaning and settling process for multiple times until the pH value of the upper layer solution is neutral, and filtering to obtain a sediment;
placing the sediment in a high-temperature drying box to dry for 3h at 160 ℃, then placing the dried carbon powder in a crusher to crush for 20 s, crushing for 5 times, pouring the crushed carbon powder into a glass container to store for later use, and obtaining pretreated carbon powder with the particle size range of 300-450 mu m;
2) respectively weighing 40g of pretreated carbon powder, 180g of formic acid and 1000g of ethylene glycol by using an analytical balance, uniformly mixing, placing in a water bath environment at 0 ℃, sequentially carrying out magnetic stirring and ultrasonic dispersion (ultrasonic frequency is 50kHz, power is 600W) for 20min respectively, and then adding into a reaction kettle together with 400g of 40 wt% chloroplatinic acid aqueous solution;
washing the pipeline and the beaker by using 3000g of ethylene glycol solution, adding the ethylene glycol solution into the reactor, adding 750g of deionized water into the reactor, washing the beaker and the pipeline, adding the deionized water into the reaction kettle, setting the stirring speed to be 300r/min, introducing nitrogen into the reaction kettle at the nitrogen flow rate of 1L/min, introducing the nitrogen for 40min, and stabilizing the temperature in the reaction kettle to 60 +/-2 ℃;
weighing 1500g of sodium carbonate powder by using an electronic balance, adding the sodium carbonate powder into 5000g of water, heating the mixture to 80 ℃ in a water bath kettle, continuously stirring the mixture by using a glass rod until the mixture is completely dissolved, and then quickly adding the mixture into a reaction kettle;
stirring and reacting for 3 hours under the reaction conditions of 60 +/-2 ℃ of temperature in the kettle, 1.5L/min of nitrogen flow and 300r/min of stirring rotation speed to obtain black reaction product mixed liquor;
3) transferring the reaction product mixed solution from the reaction kettle to a container, adding 2000g of 20 wt% dilute sulfuric acid solution to enable the pH of the solution to reach 4, adding 5 times volume of deionized water relative to the reaction product mixed solution, stirring and mixing uniformly, and then standing and settling; pumping the supernatant into Buchner funnel, filtering, mixing the residue with the precipitate, adding deionized water, washing, precipitating, and repeating for 10 times until the conductivity of the supernatant is less than 5 μ S cm-1；
After the finally obtained sediment is filtered by a Buchner funnel, the sediment is heated and dried in a drying furnace in nitrogen atmosphere at the temperature of 130 ℃, the nitrogen flow is 0.6L/min, and the heating time is 1 h; and then vacuum drying is carried out for 2h at 180 ℃, and the carbon-supported platinum nanoparticle catalyst with the concentration of 60% is obtained after uniform grinding by an agate mortar.
The electrochemical performance of the catalysts was tested using a Rotating Disk Electrode (RDE). FIGS. 1 and 2 show the results of electrochemical tests (CV and LSV) on the catalyst prepared in this example; fig. 3 and 4 show TEM and particle size statistics of the catalyst prepared in this example. The electrochemically active area (ECSA) of the prepared catalyst was calculated to be 67.87m2The Mass Activity (MA) was 95.14mA/mg, the average particle diameter of the catalyst was 3.57nm, and the performance was substantially equivalent to that of a commercial platinum-carbon catalyst (JM-Pt/C-60%, reference value ECSA 65 m)2Per g, MA about 80 mA/mg).
Comparative example 1:
compared with the example 1, the difference is that no formic acid is added in the step 2), and the rest is the same as the example 1.
Comparative example 2:
the process is the same as example 1 except that no dilute sulfuric acid is added in step 3) as compared with example 1.
Comparative example 3:
compared with example 1, except that the number of washing and settling repetitions in the step 3) was reduced to 3, the conductivity of the obtained supernatant was 43. mu.S-cm-1Otherwise, the same procedure as in example 1 was repeated.
Referring to the electrochemical properties and physical properties of the catalyst obtained in example 1 and the catalysts obtained in comparative examples 1 to 3, the results are shown in Table 1.
Table 1 comparison of the performance of the catalysts obtained in example 1 with those obtained in comparative examples 1 to 3
Example 2:
the same as in example 1 was repeated except that the aqueous sulfuric acid solution added in step 1) was 5% by weight and used in an amount of 2000g, as compared with example 1.
Example 3:
compared with the embodiment 1, the difference is only that in the heating and stirring process of the step 1), the heating temperature is 60-80 ℃, and the heating time is 1 h; before crushing, the drying temperature is 180 ℃, the drying time is 2 hours, and the rest is the same as the example 1.
Example 4:
compared with the example 1, the difference is only that in the step 2), the dosage of the chloroplatinic acid aqueous solution is 400g, the concentration is 25 wt%, the mass ratio of the chloroplatinic acid to the formic acid is 1.2:1, the mass ratio of the chloroplatinic acid to the pretreated carbon powder is 1:0.25, the mass ratio of the formic acid to the deionized water is 1:4, the mass ratio of the ethylene glycol to the deionized water is 3:1, and the rest is the same as the example 1.
Example 5:
compared with the embodiment 1, the difference is only that in the step 2), the ultrasonic time is 10 min; the magnetic stirring process is carried out in a nitrogen atmosphere, the nitrogen flow is 0.6L/min, the stirring speed is 200r/min, and the time is 30 min; the rest is the same as example 1.
Example 6:
compared with the example 1, the difference is only that in the step 2), the temperature in the reaction kettle is 80 ℃ before the sodium carbonate solution is added; the rest is the same as example 1.
Example 7:
compared with the example 1, the difference is only that in the step 2), the temperature in the reaction kettle is 80 ℃ before the sodium carbonate solution is added; adding 3000g of sodium carbonate into a sodium carbonate solution, wherein the concentration of the solution is 40 wt%; in the reaction process, the reaction temperature is 80 ℃, the nitrogen flow is 1L/min, the stirring speed is 300r/min, and the reaction time is 5 h; the rest is the same as example 1.
Example 8:
compared with the example 1, the difference is only that in the step 3), the concentration of the dilute sulphuric acid is 30wt percent, and the pH value of the solution is adjusted to 3; after the final sediment is filtered, heating and drying the sediment in a drying furnace in the nitrogen atmosphere at the temperature of 110 ℃, wherein the nitrogen flow is 0.6L/min, and the heating time is 1 h; then vacuum drying for 2h at 190 ℃; the rest is the same as example 1.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for batch preparation of a catalyst for a fuel cell, the method comprising:
mixing a carrier, formic acid and ethylene glycol, heating and reacting with water, a chloroplatinic acid solution and a sodium carbonate solution in an inert gas atmosphere, and carrying out aftertreatment on the obtained reaction product mixed solution to obtain the carbon-supported nano platinum particle catalyst.
2. The batch preparation method of a fuel cell catalyst according to claim 1, wherein the carrier comprises at least one of carbon nanospheres, carbon nanoclusters, carbon nanotubes, graphene, mesoporous carbon, macroporous carbon, graphitized carbon, nitrogen-doped carbon material, boron-doped carbon material, sulfur-doped carbon material, silicon carbide, titanium dioxide, tungsten oxide, and zinc oxide.
3. The batch preparation method of a fuel cell catalyst according to claim 2, wherein when the carrier is a carbon material, the carrier is pre-treated and then mixed with formic acid and ethylene glycol in step 1), wherein the pre-treatment method comprises:
and mixing the carbon material with ethanol and sulfuric acid solution, and sequentially heating, stirring, settling, washing and drying to obtain the pretreated carrier.
4. The batch preparation method of a fuel cell catalyst according to claim 3, wherein the concentration of the sulfuric acid solution is 5 to 30 wt%, the mass ratio of the carbon material to the sulfuric acid solution is (1-5):20, and the mass ratio of the ethanol to the sulfuric acid solution is 1 (5-10);
in the heating and stirring process, the stirring temperature is 60-80 ℃, and the stirring time is 1-3 h;
in the drying process, the drying temperature is 160-;
as a preferred technical scheme, the mixing process of the carrier, the formic acid and the ethylene glycol comprises ultrasonic dispersion, wherein the ultrasonic frequency is 5-50kHz, the ultrasonic power is 500-800W, and the ultrasonic time is 3-30 min.
5. The batch preparation method of a fuel cell catalyst according to claim 3, wherein the concentration of the chloroplatinic acid solution is 25 to 75 wt%, the mass ratio of the chloroplatinic acid to the formic acid is (0.8 to 1.2):1, the mass ratio of platinum to the carbon material in the chloroplatinic acid is 1 (0.56 to 3.57), the mass ratio of ethylene glycol to water is (3 to 6):1, and the mass ratio of water to formic acid is (4 to 5): 1.
6. The batch preparation method of a fuel cell catalyst according to claim 5, wherein the mass ratio of sodium carbonate to water in the sodium carbonate solution is (5-8):20, and the mass ratio of the sodium carbonate solution to formic acid is (30-50): 1.
7. The batch preparation method of a fuel cell catalyst as recited in claim 3, wherein the reaction temperature is 60-90 ℃ and the reaction time is 3-6h during the heating reaction, the reaction atmosphere is a continuously flowing nitrogen atmosphere, the nitrogen flow rate is 1.5-2.0L/min, and the stirring rotation rate is 200-300 rpm.
8. The batch preparation method of a catalyst for fuel cells according to claim 1, wherein the post-treatment process comprises: and mixing the reaction product mixed solution with an acid solution, standing and settling, and sequentially washing, filtering and drying the sediment to obtain the carbon-supported nano platinum particle catalyst.
9. The batch preparation method of a fuel cell catalyst according to claim 8, wherein the acidic solution is a 20-30 wt% dilute sulfuric acid solution, and after the reaction product mixture is mixed with the acidic solution, the pH is adjusted to 3-5;
after multiple water washing, the conductivity of the supernatant is not more than 5 muS-cm-1。
10. The batch preparation method of a catalyst for a fuel cell according to claim 8, wherein the drying process comprises: placing the filter residue in an inert gas atmosphere with the flow rate of 0.6-0.8L/min, and heating and drying for 0.5-1h at the temperature of 110-; and then vacuum drying is carried out for 2-4h at the temperature of 180 ℃ and 200 ℃, thus obtaining the carbon-supported nano platinum particle catalyst.
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