CN113437311A - Preparation method of Pt-M spherical catalyst for fuel cell - Google Patents
Preparation method of Pt-M spherical catalyst for fuel cell Download PDFInfo
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- CN113437311A CN113437311A CN202110565956.6A CN202110565956A CN113437311A CN 113437311 A CN113437311 A CN 113437311A CN 202110565956 A CN202110565956 A CN 202110565956A CN 113437311 A CN113437311 A CN 113437311A
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- acac
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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
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/9041—Metals or alloys
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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
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
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- 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 discloses a preparation method of a Pt-M spherical catalyst for a fuel cell, which selects SiO2Dispersing with PDDA in pure water, centrifuging, and mixing the separated powder with Pt (acac)2And adding the compound of the metal M into tetraethyleneglycol, and dissolving by ultrasonic wave. After the reaction was heated, it was centrifuged and washed with ethanol, and then dried at room temperature. Finally removing SiO2And obtaining the Pt-M spherical catalyst. The catalyst for the fuel cell prepared by the invention is added with the alloy M, so that the consumption of noble metals is reduced, the cost is reduced, and meanwhile, the specific surface area of the catalyst can be effectively increased by virtue of the spherical structure, so that the catalyst has better catalytic activity.
Description
Technical Field
The invention relates to the technical field of catalyst production, in particular to a preparation method of a Pt-M spherical catalyst for a fuel cell.
Background
The shortage of energy sources and the depletion of traditional fossil fuels bring serious challenges to human beings, and green new energy sources are one of the ways for effectively solving the energy crisis. Among them, hydrogen is attracting attention because it has no environmental pollution and is widely available. The fuel cell is a device for directly converting hydrogen energy into electric energy, and the technical development of the fuel cell can effectively improve the energy conversion efficiency.
The main occurrence in fuel cells is the hydrogen oxidation reaction and the oxygen reduction reaction, both of which need to be catalyzed by a catalyst. The catalysts currently used by fuel cells are mainly the noble metal platinum and varying percentages of platinum carbon catalyst. However, the slow reaction kinetics of the oxygen reduction reaction throughout the reaction limits the fuel cell conversion efficiency. Large amounts of catalyst are typically required for catalysis, but the progress of commercial use of the entire cell is limited due to the expensive price and low reserves of platinum. Therefore, the preparation of low-loading high-activity catalysts is an important means for commercializing the catalysts.
Pt is still irreplaceable due to the combination of catalytic performance and service life at the present stage. However, pure Pt or PtC catalysts have significant drawbacks: firstly, the common Pt catalyst is easy to agglomerate, the specific surface area is reduced after agglomeration, and the catalytic activity is reduced; secondly, when the battery is stopped, the corrosion of C is easily caused, so that Pt on the PtC is agglomerated in a larger range, the activity is reduced, and the service life of the catalyst is also shortened.
Disclosure of Invention
The invention aims to provide a preparation method of a Pt-M spherical catalyst for a fuel cell, which has simple process and controllable cost.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a Pt-M spherical catalyst for a fuel cell comprises the following steps:
(1) mixing SiO2Mixing the powder, pure water and PDDA, and performing ultrasonic dispersion;
(2) adding 100mg of solid powder obtained after centrifugal separation into 100-150mL of alcohol for ultrasonic dispersion to obtain alcohol dispersion liquid;
(3) mixing Pt (acac)2And 100mg-500mg of the mixture of the metal M compound is added into the alcohol dispersion liquid obtained in the step (2), and ultrasonic dispersion is carried out again;
(4) transferring the liquid prepared in the step (3) into a three-mouth bottle, heating, condensing, refluxing and cooling to room temperature;
(5) carrying out centrifugal cleaning on the liquid prepared in the step (4) by adopting ethanol, and then drying at room temperature to obtain powder;
(6) adding the powder obtained by drying in the step (5) into NaOH solution, stirring for 1-4 hours at the temperature of 60-80 ℃ to remove SiO2Obtaining a Pt-M alloy catalyst solution;
(7) and centrifugally cleaning the Pt-M alloy catalyst solution by using deionized water, ultrasonically dispersing, and drying at room temperature to obtain the Pt-M spherical catalyst.
In the invention, acetylacetone compounds are selected as compounds of Pt and metal M, and the inventor researches show that acac bonding energy is high, Pt-M is firmly combined, the bonding force is good, and a stable microspherical shape is easier to form, and the size of the final catalyst microsphere formed by acac is about 300nm, but the size of Pt particles is about 5-10nm, and the size of the Pt particles is in a state of optimally playing the catalytic activity.
Preferably, SiO in the step (1)2The mass ratio of the PDDA to the PDDA is 1:4-1:16, and the mass ratio of the PDDA to the pure water is 1:17-1: 30. The invention firstly adopts PDDA (poly diallyl dimethyl ammonium chloride) to treat SiO2PDDA acts like a surfactant, allowing the surface of the silica to create active sites for the attachment of Pt and metal M.
Preferably, in the step (2), the alcohol is tetraethylene glycol or a mixture of tetraethylene glycol and oleic acid and oleamide.
Preferably, the mixture of tetraethylene glycol with oleic acid and oleamide is prepared from tetraethylene glycol: oleic acid: the mass ratio of oleamide =100:1-3: 1-3.
Preferably, the compound of metal M in the step (3) is M (acac)2WhereinM is one of Ni, Fe, Cu, Ag, V, Mn, Co, Ru, Pd and Ce, Pt (acac)2:M(acac)2Is =1-3: 1.
Preferably, in the step (4), the reaction mixture is heated to 200-380 ℃ for condensation reflux for 2-8 hours.
Preferably, in the step (5), the mass concentration of ethanol is 95% or more.
Preferably, in the step (6), the concentration of the NaOH solution is 3mol/L-10 mol/L.
The invention has the beneficial effects that:
1) the alloy M is added, so that the use amount of the noble metal Pt is reduced, and the preparation cost is reduced;
2) the catalyst structure is hollow spherical, so that the specific surface area of the catalyst is effectively increased, the utilization rate is improved, C is not used as a carrier, and the catalyst agglomeration caused by C corrosion in the stopping and starting process of the battery is prevented;
3) the Pt-M spherical catalyst effectively improves the catalytic efficiency.
Drawings
FIG. 1 is a schematic flow diagram of the present invention.
FIG. 2 is a microscopic morphology of the Pt-Ni spherical catalyst prepared in example 1.
FIG. 3 is a cyclic voltammogram of the Pt-Ni spherical catalyst prepared in example 1 under 0.1M perchloric acid; the scanning interval is-0.22V to 0.955V (vs. SCE), and the scanning speed is 20 mV/s.
FIG. 4 is an oxygen reduction curve of the Pt-Ni spherical catalyst prepared in example 1 under 0.1M perchloric acid; the scanning interval is-0.22V to 0.755V (vs. SCE), the scanning speed is 20mV/s, and the electrode rotation speed is 1600 rpm.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
General description of the embodiments
A preparation method of a Pt-M spherical catalyst for a fuel cell comprises the following steps:
(1) mixing SiO2Mixing the powder, pure water and PDDA, and performing ultrasonic dispersion; SiO 22The mass ratio of the PDDA to the PDDA is 1:4-1:16, and the mass ratio of the PDDA to the pure water is 1:17-1: 30.
(2) Adding 100mg of solid powder obtained after centrifugal separation into 100-150mL of alcohol for ultrasonic dispersion to obtain alcohol dispersion liquid; the alcohol is tetraethylene glycol or a mixture of tetraethylene glycol with oleic acid and oleamide. Mixtures of tetraethylene glycol with oleic acid and oleamide are prepared from tetraethylene glycol: oleic acid: the mass ratio of oleamide =100:1-3: 1-3.
(3) Mixing Pt (acac)2Adding 100-500 mg of a mixture of the metal M and the compound of the metal M into the alcohol dispersion liquid obtained in the step (2), and performing ultrasonic dispersion again; the compound of metal M is M (acac)2Wherein M is one of Ni, Fe, Cu, Ag, V, Mn, Co, Ru, Pd and Ce, Pt (acac)2:M(acac)2Is =1-3: 1.
(4) Transferring the liquid prepared in the step (3) into a three-mouth bottle, heating to 200-380 ℃, condensing and refluxing for 2-8 hours, and cooling to room temperature;
(5) carrying out centrifugal cleaning on the liquid prepared in the step (4) by adopting ethanol, and then drying at room temperature to obtain powder; the mass concentration of the ethanol is more than 95 percent.
(6) Adding the powder obtained by drying in the step (5) into NaOH solution, stirring for 1-4 hours at the temperature of 60-80 ℃ to remove SiO2Obtaining a Pt-M alloy catalyst solution; the concentration of the NaOH solution is 3-10 mol/L.
(7) And centrifugally cleaning the Pt-M alloy catalyst solution by using deionized water, ultrasonically dispersing, and drying at room temperature to obtain the Pt-M spherical catalyst.
Example 1:
the flow chart of the preparation of the Pt-M spherical catalyst is shown in figure 1. Mixing 100mg of SiO2And 500mg of PDDA were added to 10ml of water, and ultrasonic dispersion was carried out at room temperature for 20 min. Centrifuging with deionized water for 3 times, removing supernatant to obtain powder100mg of the powder is added into 100ml of tetraethylene glycol for ultrasonic dispersion, and then the mixture is mixed according to the proportion of 1: nickel acetylacetonate and platinum acetylacetonate were weighed and mixed at 1 (molar ratio), and 260mg of the mixture was weighed and added to tetraethylene glycol, followed by ultrasonic dispersion.
The liquid was transferred to a three-necked flask and heated to 230 ℃ and condensed at reflux for 2 hours. The liquid after the reaction was cooled to room temperature and centrifuged, and then dried at room temperature to form a powder sample. Preparing 200ml of 5mol/L NaOH solution to dissolve the powder, stirring and heating the solution in a water bath at 70 ℃ for 1 hour, then centrifugally cleaning the solution by using deionized water, dispersing the solution by using ultrasonic waves, then centrifugally separating the solution, and finally drying the solution at room temperature to form Pt-Ni spherical catalyst powder. The powder micro-morphology is shown in fig. 2.
The overall size of the Pt-Ni spherical fuel cell catalyst prepared by the embodiment is about 300nm, the cost is reduced by about 3 times compared with that of the common commercial catalyst, and the loading capacity can be reduced by 0.3mg/cm2About, the ECSA of the Pt-Ni spherical catalyst was 27.3M by measuring the CV curve under 0.1M perchloric acid2(ii)/g; the Pt-Ni spherical catalyst MA obtained by measuring an LSV curve under 0.1M perchloric acid can reach 0.53A/mgPtAbout 3 times the activity of commercial catalysts. The prepared Pt-Ni realizes the preparation of the Pt-based catalyst with high activity and low loading.
Example 2:
80mg of SiO2And 300mg of PDDA were added to 10ml of water, and ultrasonic dispersion was carried out at room temperature for 15 min. After 3 centrifugal washes with deionized water, the supernatant was removed to obtain a powder, which was added to 130ml of tetraethylene glycol and mixed according to a 1: 1.2 (molar ratio) iron acetylacetonate and platinum acetylacetonate were weighed and mixed, and 275mg of the mixture was added to tetraethylene glycol and ultrasonically dispersed.
The liquid was transferred to a three-necked flask and heated to 260 ℃ and condensed at reflux for 2.5 hours. The liquid after the reaction was cooled to room temperature and centrifuged, and then dried at room temperature to form a powder sample. Preparing 200ml of 5mol/L NaOH solution to dissolve the powder, stirring and heating the solution in a water bath at 70 ℃ for 1 hour, then centrifugally cleaning the solution by using deionized water, dispersing the solution by using ultrasonic waves, then centrifugally separating the solution, and finally drying the solution at room temperature to form Pt-Fe spherical catalyst powder.
The overall size of the Pt-Fe spherical fuel cell catalyst prepared by the embodiment is about 300nm, the cost is reduced by about 3 times compared with that of the common commercial catalyst, and the loading capacity can be reduced by 0.3mg/cm2About 26.6M ECSA months measured in 0.1M perchloric acid2The MA can reach 0.5A/mgPtAbout 3 times the activity of commercial catalysts. The prepared Pt-Fe realizes the preparation of the Pt-based catalyst with high activity and low loading.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (8)
1. A preparation method of a Pt-M spherical catalyst for a fuel cell is characterized by comprising the following steps:
(1) mixing SiO2Mixing the powder, pure water and PDDA, and performing ultrasonic dispersion;
(2) centrifuging to obtain solid powder, adding 100mg of the solid powder into 100mL-150mL of alcohol, and performing ultrasonic dispersion to obtain alcohol dispersion;
(3) mixing Pt (acac)2And 100mg-500mg of the mixture of the metal M compound is added into the alcohol dispersion liquid obtained in the step (2), and ultrasonic dispersion is carried out again;
(4) transferring the liquid prepared in the step (3) into a three-mouth bottle, heating, condensing, refluxing and cooling to room temperature;
(5) carrying out centrifugal cleaning on the liquid prepared in the step (4) by adopting ethanol, and then drying at room temperature to obtain powder;
(6) adding the powder obtained by drying in the step (5) into NaOH solution, stirring for 1-4 hours at the temperature of 60-80 ℃ to remove SiO2Obtaining a Pt-M alloy catalyst solution;
(7) and centrifugally cleaning the Pt-M alloy catalyst solution by using deionized water, ultrasonically dispersing, and drying at room temperature to obtain the Pt-M spherical catalyst.
2. The method according to claim 1, wherein SiO in the step (1)2The mass ratio of the PDDA to the PDDA is 1:4-1:16, and the mass ratio of the PDDA to the pure water is 1:17-1: 30.
3. The method according to claim 1, wherein in the step (2), the alcohol is tetraethylene glycol or a mixture of tetraethylene glycol with oleic acid and oleamide.
4. The process of claim 3, wherein the mixture of tetraethylene glycol with oleic acid and oleamide is prepared from tetraethylene glycol: oleic acid: the mass ratio of oleamide =100:1-3: 1-3.
5. The process according to claim 1, wherein the compound of metal M in step (3) is M (acac)2Wherein M is one of Ni, Fe, Cu, Ag, V, Mn, Co, Ru, Pd and Ce, Pt (acac)2:M(acac)2Is =1-3: 1.
6. The method as claimed in claim 1, wherein in the step (4), the heating is carried out at 380 ℃ for 2-8 hours under reflux condensation.
7. The production method according to claim 1, wherein the mass concentration of ethanol in the step (5) is 95% or more.
8. The method according to claim 1, wherein in the step (6), the concentration of the NaOH solution is 3mol/L to 10 mol/L.
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