CN112151818A - Alkaline system direct methanol fuel cell anode catalyst and preparation method thereof - Google Patents
Alkaline system direct methanol fuel cell anode catalyst and preparation method thereof Download PDFInfo
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- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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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 relates to an alkaline system direct methanol fuel cell anode catalyst and a preparation method thereof, wherein polyvinyl alcohol-polyaniline conductive hydrogel is used as a carrier, is impregnated with soluble nickel salt, and is calcined in an inert atmosphere to obtain an elemental nickel nanocrystalline composite material which is wrapped by a nitrogen-containing carbon material and contains 2-8 wt% of elemental nickel. The invention adopts a brand new catalyst carrier loaded with transition metal nickel to replace the traditional noble metal, regulates the electronic structure of the catalyst by doping heteroatom, improves the catalytic activity and electrode conductivity of the catalyst, and has excellent electrochemical reaction activity.
Description
Technical Field
The invention relates to a fuel cell anode catalyst, in particular to a non-noble metal-based carbon material anode catalyst for a direct methanol fuel cell in an alkaline system and a preparation method thereof. The catalyst prepared by the invention can be used for electrochemical catalytic oxidation of methanol.
Background
The large consumption of fossil fuels causes problems such as energy crisis, global warming, environmental pollution, and the like, and the development of new energy and the improvement of energy conversion efficiency are urgently required.
A Direct Methanol Fuel Cell (DMFC) is a fuel cell that uses methanol as a fuel. Because the methanol fuel is easy to produce, store and transport in a large scale, the final products of the electrocatalytic oxidation of methanol are carbon dioxide and water, and the DMFC has the advantages of high energy conversion efficiency, strong reliability, cleanness, easy start and the like as a potential energy supply device.
Noble metals such as Pt, Pd, Ru and the like have good catalytic activity and are widely applied to anode catalysts of DMFC. However, such noble metal-based catalysts are easily poisoned by intermediate products such as CO generated during electrolysis, and the high cost and poisoning effect thereof directly affect the large-scale commercial promotion of DMFC, and there is an urgent need to develop a methanol oxidation anode catalyst with low price, high catalytic activity and high stability.
Among the non-noble metal-based catalysts, nickel-based catalysts such as Ni/3D-graphene [ Three-dimensional porous graphene supported Ni nanoparticles with enhanced catalytic performance for Methanol oxidation, int. J. Hydrogen Energy, 42(2017), 11206-11214, are inexpensive due to the abundance of nickel in the earth's crust.]、NiO NTs-400[Self-template synthesis of defect-rich NiO nanotubes as efficient electrocatalysts for methanol oxidation reaction, Nanoscale, 11(2019), 19783-19790.]And VO-rich NiO nanosheets[Oxygen vacancies confined in ultrathin nickel oxide nanosheets for enhanced electrocatalytic methanol oxidation, Appl. Catal., B, 244(2019), 1096-1102.]Etc. have proven to be effective methanol anode electrocatalysts.
Generally, in order to improve conductivity and dispersion of the nickel active component, it is generally selected to support nickel on a carbon material such as carbon black, carbon nanotube, graphene, or the like. However, the traditional nickel-based catalyst has complex preparation method and preparation process, and the uniform dispersion degree of the active component nickel is not high, which directly influences the electrochemical reaction activity of methanol oxidation.
For example, the Ni/3D-graphene catalysts of the above documents are at a voltage of 1.6V (vs RHE)The current density of methanol oxidation is only 64.6mA ∙ cm−2The methanol oxidation current density of the NiO NTs-400 catalyst under the voltage of 1.5V (vs RHE) is only 24.3mA ∙ cm−2，VOMethanol oxidation current density of-rich NiO nanosheets catalyst at 1.5V (vs RHE) voltage of only 85.3mA ∙ cm−2. Therefore, there is a need to find a simple method for combining an active nickel component with a carbon material having good conductivity, which has high electrocatalytic activity for methanol oxidation.
Disclosure of Invention
The invention aims to provide an alkaline system direct methanol fuel cell anode catalyst and a preparation method thereof, which improve the catalytic activity of the catalyst and the electrical conductivity of an electrode by doping heteroatom to regulate and control the electronic structure of the catalyst.
The alkaline system direct methanol fuel cell anode catalyst is a simple substance nickel nanocrystalline composite material which is obtained by using polyvinyl alcohol-polyaniline conductive hydrogel as a carrier, impregnating soluble nickel salt with the carrier, and calcining the carrier in an inert atmosphere, wherein the simple substance nickel is wrapped by a nitrogen-containing carbon material, and the content of the simple substance nickel is 2-8 wt%.
The polyvinyl alcohol-polyaniline conductive hydrogel is prepared by taking triaminophenylboronic acid hydrochloride (ABA), Aniline (AN) and polyvinyl alcohol (PVA) as raw materials and performing polymerization reaction in AN aqueous solution system containing initiator Ammonium Persulfate (APS).
The preparation method of the alkaline system direct methanol fuel cell anode catalyst is characterized by adding hydrochloric acid solution of triaminophenylborate hydrochloride and aniline into polyvinyl alcohol aqueous solution, uniformly dissolving, cooling to 0 ℃, dropwise adding ammonium persulfate solution, carrying out polymerization reaction to obtain polyvinyl alcohol-polyaniline conductive hydrogel, taking the polyvinyl alcohol-polyaniline conductive hydrogel as a carrier, fully soaking the polyvinyl alcohol-polyaniline conductive hydrogel in soluble nickel salt solution, taking out, cleaning, drying, calcining at 300-800 ℃ under inert atmosphere, cooling, crushing and grinding to obtain the Ni-N-C composite catalyst.
Furthermore, the molar ratio of the used triaminophenylboronic acid hydrochloride to the used aniline used as the raw material for the polymerization reaction is 0.01-0.1: 1, and the used amount of the polyvinyl alcohol is 30-600 times of the mass of the triaminophenylboronic acid hydrochloride.
More specifically, the polymerization reaction is carried out at room temperature, and the reaction time is preferably 6-30 h.
In the above preparation method of the present invention, preferably, the mass concentration of the polyvinyl alcohol aqueous solution is 8 to 12 wt%.
More specifically, according to the present invention, after the hydrochloric acid solution of triaminophenylborate hydrochloride and aniline are added to the polyvinyl alcohol aqueous solution, the temperature is raised to 55 ℃, and the mixture is stirred and dissolved, such that a solution with uniform dissolution is obtained.
Further, the prepared polyvinyl alcohol-polyaniline conductive hydrogel is soaked in 0.5-7 mol/L soluble nickel salt solution, and the preferred soaking time is 3-30 h.
The invention preferably adopts a freeze drying mode to dry the polyvinyl alcohol-polyaniline conductive hydrogel loaded with nickel ions. Freeze-drying helps to preserve the porous nature characteristic of hydrogels to yield elemental nickel nanocrystalline composites encapsulated by nitrogen-containing carbon materials after calcination in an inert atmosphere.
Wherein the calcination time is preferably 1-5 h.
More specifically, the polyvinyl alcohol-polyaniline conductive hydrogel impregnated with nickel ions is heated to 300-800 ℃ from room temperature at the speed of 1-5 ℃/min and then calcined.
The invention adopts polyvinyl alcohol-polyaniline conductive hydrogel as a brand new catalyst carrier, and adopts a simple impregnation method to load transition metal nickel to replace the traditional noble metal, and the nitrogen-containing carbon material wrapped elementary nickel nanocrystalline composite material is obtained by calcination. The catalyst is used as an alkaline system direct methanol fuel cell anode catalyst and has excellent electrochemical reaction activity.
The catalyst prepared by the invention is dispersed by absolute ethyl alcohol, and then directly coated on the surface of hydrophilic conductive carbon cloth, and can be used as a working electrode after being dried, and no binder is used, so that the existence of an inactive area can be avoided, and the working electrode has better conductivity.
The invention further improves the catalytic activity of the Ni-N-C composite catalyst by doping heteroatom N in the catalyst to regulate and control the electronic structure of the catalyst. The activity of the methanol electrochemical oxidation reaction of the Ni-N-C composite catalyst prepared by the method is tested by adopting a cyclic voltammetry method, and the peak current density of 0.6V in the mixed electrolyte of 1M potassium hydroxide and 1M methanol solution reaches 146.64mA ∙ cm at the scanning rate of 50mV/s2Has obvious catalytic effect on methanol. Meanwhile, the current density is still maintained to be 132.2mA ∙ cm under the test of a timing current method i-t of 2h under the voltage of 0.6V2The retention rate was 90.15%.
Drawings
FIG. 1 is an X-ray diffraction pattern of Ni-N-C composite catalyst powder prepared in example 1.
FIG. 2 is a plot of cyclic voltammograms of the catalyst prepared in example 1 in a solution of 1M potassium hydroxide and 1M potassium hydroxide +1M methanol.
FIG. 3 is a graph of a 2h chronoamperometric i-t test for the catalyst prepared in example 1.
Detailed Description
The following examples further describe embodiments of the present invention. The following examples are only for more clearly illustrating the technical solutions of the present invention so as to enable those skilled in the art to better understand and utilize the present invention, and do not limit the scope of the present invention. The following examples of the present invention are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Example 1.
0.0364g (0.21mmol) of triaminophenylboronic acid hydrochloride (ABA) is weighed and dissolved in 835 muL of 6mol/L hydrochloric acid solution to prepare ABA solution.
Sequentially adding the ABA solution, 274 muL (3mmol) Aniline (AN) and 241 muL deionized water into 2mL 10wt% polyvinyl alcohol (PVA) solution, heating in a water bath at 55 ℃, stirring for 30min, placing in AN ice water bath after the solution is clear, cooling to 0 ℃, dropwise adding 1.65mL 2mol/L Ammonium Persulfate (APS) solution, quickly stirring uniformly, pouring into a mold, and carrying out polymerization reaction for 12h at normal temperature to prepare the polyvinyl alcohol-polyaniline conductive hydrogel polymer film.
Washing the formed polymer film with deionized water, soaking in 5mol/L nickel chloride solution for 18h, taking out, washing with deionized water, freeze-drying for 10h, placing in a tubular reaction furnace, and reacting in N2Raising the temperature from room temperature to 500 ℃ at the speed of 2 ℃/min for 120min under the atmosphere, and then carrying out N reaction2Cooling to room temperature under protection.
Taking out the sample, grinding uniformly, and preparing the Ni-N-C catalyst.
The active material and the corresponding crystal face in the catalyst prepared above were tested by powder X-ray diffraction analysis technique to obtain the diffraction pattern shown in fig. 1. The active material in the catalyst was confirmed to be elemental nickel by comparing it with JCPDS card number 04-0850, a standard joint Committee for powder diffraction standards, which corresponds to three different crystal phases of elemental nickel (111), (200), (220) at diffraction angles 2 theta = 44.5 °, 51.8 ° and 76.4 °, respectively.
Example 2.
0.0242g (0.14mmol) of triaminophenylboronic acid hydrochloride (ABA) is weighed and dissolved in 835 mu L of 6mol/L hydrochloric acid solution to prepare ABA solution.
Sequentially adding the ABA solution, 183 muL (2mmol) Aniline (AN) and 882 muL deionized water into 2.5mL of 8wt% polyvinyl alcohol (PVA) solution, stirring for 30min under the heating of water bath at 55 ℃, placing the solution in ice water bath after the solution is clear, cooling to 0 ℃, dropwise adding 1.10mL of 2mol/L Ammonium Persulfate (APS) solution, quickly stirring uniformly, pouring the solution into a mold, and carrying out polymerization reaction for 12h at normal temperature to prepare the polyvinyl alcohol-polyaniline conductive hydrogel polymer film.
Washing the formed polymer film with deionized water, soaking in 3mol/L nickel chloride solution for 18h, taking out, washing with deionized water, freeze-drying for 10h, placing in a tubular reaction furnace, and reacting in N2Raising the temperature from room temperature to 400 ℃ at the speed of 2 ℃/min for 120min under the atmosphere, and then carrying out N reaction2Cooling to room temperature under protection.
Taking out the sample, grinding uniformly, and preparing the Ni-N-C catalyst.
Example 3.
0.0303g (0.175mmol) of triaminophenylboronic acid hydrochloride (ABA) is weighed and dissolved in 835 mu L of 6mol/L hydrochloric acid solution to prepare an ABA solution.
Sequentially adding the ABA solution, 229 muL (2.5mmol) Aniline (AN) and 561 muL deionized water into 2mL of 12wt% polyvinyl alcohol (PVA) solution, stirring for 30min under the heating of water bath at 55 ℃, placing the solution in ice water bath after the solution is clear, cooling to 0 ℃, dropwise adding 1.38mL of 2mol/L Ammonium Persulfate (APS) solution, quickly stirring uniformly, pouring the solution into a mold, and carrying out polymerization reaction for 12h at normal temperature to prepare the polyvinyl alcohol-polyaniline conductive hydrogel polymer film.
Washing the formed polymer film with deionized water, soaking in 5mol/L nickel chloride solution for 18h, taking out, washing with deionized water, freeze-drying for 10h, placing in a tubular reaction furnace, and reacting in N2Raising the temperature from room temperature to 600 ℃ at the speed of 2 ℃/min for 120min under the atmosphere, and then carrying out N reaction2Cooling to room temperature under protection.
Taking out the sample, grinding uniformly, and preparing the Ni-N-C catalyst.
Example 1 is applied.
Weighing 5mg of the Ni-N-C catalyst prepared in the example 1, placing the Ni-N-C catalyst in a centrifuge tube, adding 50 muL of absolute ethyl alcohol, ultrasonically dispersing for 15min, sucking 7.5 muL by using a pipette gun, uniformly dropwise adding the catalyst on the surface of hydrophilic carbon cloth with the specification of 0.5cm multiplied by 1.5cm, and drying at room temperature.
And (3) taking the carbon cloth coated with the Ni-N-C catalyst as a working electrode, a 3cm multiplied by 4cm stainless steel sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and characterizing the electrochemical performance of the prepared Ni-N-C catalyst by adopting a three-electrode system and utilizing a cyclic voltammetry method.
Respectively taking 1M potassium hydroxide, 1M potassium hydroxide and 1M methanol mixed solution as electrolyte solution, and performing methanol electrochemical oxidation (MOR) reaction activity test by adopting Shanghai Chenghua CHI 600E electrochemical workstation.
As shown in FIG. 2, the scanning speed is 50 mv/ml in a 1M potassium hydroxide solutions, a current density of 22.8mA ∙ cm at 0.6V2(ii) a In the mixed solution of 1M potassium hydroxide and 1M methanol, the scanning speed is 50mv/s, and the corresponding current density is 146.64mA ∙ cm under the voltage of 0.6V2The catalyst has obvious catalytic effect on methanol.
According to FIG. 3, in a 1M potassium hydroxide +1M methanol mixed solution, after 2h of chronoamperometry i-t test, namely, keeping at a voltage of 0.6V, the current density is examined to change along with time, and the result shows that the current density after 2h is still kept at 132.2mA ∙ cm-2Initial current density (146.64 mA ∙ cm)-2) 90.15% of the total weight of the catalyst, indicating that the catalyst has better stability.
Some literature reports on the performance index comparison of the nickel-based catalyst are given in table 1 below. The traditional preparation method and preparation process of the nickel-based catalyst are complex, and the uniform dispersion degree of the active component nickel is not high, so that the electrochemical reaction activity of methanol oxidation is directly influenced.
As can be seen from the data in Table 1, the current density values in the cited documents are all very low in the voltage window 1.5V (vs RHE), demonstrating that the activity of methanol oxidation is not high. In order to improve the activity of the catalyst, the catalyst obtained by combining the active nickel component and the carbon material with good conductivity can obviously improve the current density value under fixed voltage, namely the activity of catalyzing and oxidizing the methanol is improved.
[1] T. J. Wang, H. Huang, X. R. Wu, H. C. Yao, F. M. Li, P. Chen, P. J. Jin, Z. W. Deng and Y. Chen, Self-template synthesis of defect-rich NiO nanotubes as efficient electrocatalysts for methanol oxidation reaction, Nanoscale, 11(2019), 19783-19790。
[2] W. Yang, X. Yang, J. Jia, C. Hou, H. Gao, Y. Mao, C. Wang,J. Lin and X. Luo, Oxygen vacancies confined in ultrathin nickel oxide nanosheets for enhanced electrocatalytic methanol oxidation Appl. Catal., B, 2019, 244, 1096–1102。
[3] Q. Luo, M. Peng, X. Sun, A.M. Asiri, Hierarchical nickel oxide nanosheet@nanowire arrays on nickel foam: an efficient 3D electrode for methanol electro-oxidation, Catal. Sci. Technol. 6 (2016) 1157-1161。
Claims (10)
1. An alkaline system direct methanol fuel cell anode catalyst is a simple substance nickel nanocrystalline composite material which is obtained by taking polyvinyl alcohol-polyaniline conductive hydrogel as a carrier, impregnating the carrier with soluble nickel salt and calcining the carrier in an inert atmosphere and is wrapped by a nitrogen-containing carbon material, wherein the content of simple substance nickel is 2-8 wt%; the polyvinyl alcohol-polyaniline conductive hydrogel is prepared by taking triaminophenylboronic acid hydrochloride, aniline and polyvinyl alcohol as raw materials and performing polymerization reaction in an aqueous solution system containing initiator ammonium persulfate.
2. The preparation method of the alkaline system direct methanol fuel cell anode catalyst according to claim 1, wherein hydrochloric acid solution of triaminophenylborate hydrochloride and aniline are added into polyvinyl alcohol aqueous solution, after the hydrochloric acid solution and aniline are dissolved uniformly, the temperature is reduced to 0 ℃, ammonium persulfate solution is dropwise added, polymerization reaction is carried out to obtain polyvinyl alcohol-polyaniline conductive hydrogel, the polyvinyl alcohol-polyaniline conductive hydrogel is used as a carrier, the polyvinyl alcohol-polyaniline conductive hydrogel is placed into soluble nickel salt solution to be fully soaked, taken out, cleaned and dried, calcined at 300-800 ℃ under inert atmosphere, cooled, crushed and ground to prepare the Ni-N-C composite catalyst.
3. The method according to claim 2, wherein the molar ratio of triaminophenylboronic acid hydrochloride to aniline is 0.01-0.1: 1, and the amount of polyvinyl alcohol is 30-600 times the mass of triaminophenylboronic acid hydrochloride.
4. The method according to claim 2, wherein the polymerization time is 6 to 30 hours.
5. The method according to claim 2, wherein the polyvinyl alcohol aqueous solution has a mass concentration of 8 to 12 wt%.
6. The preparation method according to claim 2, wherein the polyvinyl alcohol-polyaniline conductive hydrogel is immersed in 0.5-7 mol/L soluble nickel salt solution for 3-30 h.
7. The method according to claim 2, wherein the polyvinyl alcohol-polyaniline conductive hydrogel loaded with nickel ions is freeze-dried.
8. The method according to claim 2, wherein the calcination is carried out for 1 to 5 hours.
9. The method according to claim 2, wherein the polyvinyl alcohol-polyaniline conductive hydrogel impregnated with nickel ions is calcined by heating from room temperature to 300-800 ℃ at a rate of 1-5 ℃/min.
10. An alkaline system direct methanol fuel cell anode coated with the catalyst of claim 1.
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| CN113224331A (en) * | 2021-05-08 | 2021-08-06 | 中北大学 | Alkaline system direct urea fuel cell anode catalyst and preparation method thereof |
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