CN112151816B - Cobalt-based composite catalyst for direct methanol fuel cell anode and preparation method thereof - Google Patents

Cobalt-based composite catalyst for direct methanol fuel cell anode and preparation method thereof Download PDF

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CN112151816B
CN112151816B CN202011151539.9A CN202011151539A CN112151816B CN 112151816 B CN112151816 B CN 112151816B CN 202011151539 A CN202011151539 A CN 202011151539A CN 112151816 B CN112151816 B CN 112151816B
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polyvinyl alcohol
cobalt
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胡拖平
翟玫旭
安富强
高建峰
宋江锋
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North University of China
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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]
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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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    • Y02E60/50—Fuel cells

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Abstract

The invention relates to a cobalt-based composite catalyst for a direct methanol fuel cell anode and a preparation method thereof, and the cobalt-based composite catalyst is an elemental cobalt nanocrystalline composite material which is obtained by adopting weak base treated polyvinyl alcohol-polyaniline conductive hydrogel as a carrier, impregnating soluble cobalt salt with the carrier, and calcining the carrier in an inert atmosphere and is wrapped by a nitrogen-containing carbon material and contains 2-6 wt% of elemental cobalt. The invention adopts a brand new catalyst carrier loaded with transition metal cobalt 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

Cobalt-based composite catalyst for direct methanol fuel cell anode and preparation method thereof
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
Direct Methanol Fuel Cells (DMFCs) are receiving attention from researchers because of their advantages, such as simple structure, easy portability, good portability of fuels, high specific energy density, and low pollutant emissions. In recent years, DMFCs have become one of the important alternative power sources for portable and small electronic devices. And Polymer Electrolyte Fuel Cells (PEFCs) have high energy density and fuel efficiency, and thus are considered to be one of the most promising power sources.
At present, noble metals such as Pt, Pd, Ru, etc. have been widely used for anode catalysts of DMFC. But the method cannot be widely applied to industrial production due to the defects of high cost, poor poisoning resistance and the like. Therefore, the development of a non-noble metal catalyst which is cheap, excellent in stability and good in CO poisoning resistance becomes a key for improving the performance of the DMFC.
Among non-noble metal elements, cobalt is a cheap and easily available polyvalent metal, and has been widely used in various reactions such as methanol oxidation reaction and oxygen evolution reaction. For example, N (4%) -Co/CNFs [ Cobalt-doped, nitrogen-doped carbon nanoparticles as effective non-catalytic catalyst for methanol electrolysis in alkali medium, applied. Catal., A, 498(2015), 230-.]、Co-MOF-71[Novel Co-MOF/Graphene Oxide Electrocatalyst for Methanol Oxidation, Electrochim. Acta, 255(2017), 195-204.]、Co3(PO4)2[Microwave-Assisted Synthesis of Co3(PO4)2 Nanospheres for Electrocatalytic Oxidation of Methanol in Alkaline Media, Catal., 7(2017).]The isocobalt-based catalyst was proven to be an effective electrode catalyst for methanol anode catalytic reaction.
Generally, in order to prepare a high-efficiency catalyst, graphene, carbon nanotubes, g-C are generally used3N4Carbon materials such as MOFs and the like are used as a conductive framework of the catalyst, and a cobalt active component is used as an active site for catalyzing methanol reaction. However, the traditional cobalt-based catalyst has a complex preparation method, expensive raw materials and uneven dispersion of the active component cobalt, which affects the electrochemical performance of methanol oxidation and limits the wide application thereof.
For example, the precursor of the N (4%) -Co/CNFs catalyst electrode selects polyvinyl alcohol (PVA) as a template, and the methanol oxidation current density is only 101mA ∙ cm under the voltage of 1.46V (vs RHE)−2(ii) a The Co-MOF-71 catalyst electrode takes an MOFs structure as a conductive framework, and the methanol oxidation current density is only 29mA ∙ cm under the voltage of 1.65V (vs RHE)−2(ii) a And Co3(PO4)2The methanol oxidation current density of the catalyst electrode under the voltage of 1.65V (vs RHE) is only 556mA ∙ mg−2. Therefore, it is required to find a catalyst which is simple to prepare, has strong CO poisoning resistance and has good catalytic performance for methanol oxidation.
Disclosure of Invention
The invention aims to provide a cobalt-based composite catalyst for a direct methanol fuel cell anode and a preparation method of the catalyst, wherein the electronic structure of the catalyst is regulated and controlled by doping heteroatom, so that the catalytic activity of the catalyst and the electrical conductivity of an electrode are improved.
The cobalt-based composite catalyst for the direct methanol fuel cell anode is an elemental cobalt nanocrystalline composite material which is obtained by adopting weak base treated polyvinyl alcohol-polyaniline conductive hydrogel as a carrier, impregnating soluble cobalt salt with the carrier, and calcining the carrier in an inert atmosphere to wrap nitrogen-containing carbon materials, wherein the elemental cobalt content is 2-6 wt%.
The weak base treated polyvinyl alcohol-polyaniline conductive hydrogel is a hydrogel product obtained by taking triaminophenylboronic acid hydrochloride (ABA), Aniline (AN) and polyvinyl alcohol (PVA) as raw materials, carrying out polymerization reaction in AN aqueous solution system containing initiator Ammonium Persulfate (APS) to obtain the polyvinyl alcohol-polyaniline conductive hydrogel, and then placing the polyvinyl alcohol-polyaniline conductive hydrogel in a weak base solution for soaking treatment.
The polyvinyl alcohol-polyaniline conductive hydrogel which is not subjected to weak base treatment has low cobalt salt loading, and the loading after weak base treatment is obviously increased. However, the treatment of the polyvinyl alcohol-polyaniline conductive hydrogel is limited to weak alkali, and the strong alkali can damage the membrane structure of the hydrogel.
Specifically, the weak base of the present invention is preferably ammonia.
The preparation method of the cobalt-based composite catalyst for the direct methanol fuel cell anode comprises the steps of 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, soaking in weak alkali solution to obtain weak alkali treated polyvinyl alcohol-polyaniline conductive hydrogel, taking the weak alkali treated polyvinyl alcohol-polyaniline conductive hydrogel as a carrier, fully soaking in soluble cobalt salt solution, taking out, washing, drying, calcining at 300-800 ℃ under inert atmosphere, cooling, and crushing to obtain the Co-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.
Preferably, the polyvinyl alcohol-polyaniline conductive hydrogel obtained through the polymerization reaction is soaked in 0.5-2 mol/L ammonia water solution until the color of the hydrogel is changed into dark purple, emeraldine salt in the polyvinyl alcohol-polyaniline conductive hydrogel is deprotonated to form emeraldine, and polyaniline in the form can absorb metal ions more easily to prepare the non-metal catalyst.
Further, the prepared weak base treated polyvinyl alcohol-polyaniline conductive hydrogel is soaked in 0.5-3 mol/L soluble cobalt salt solution, and the preferred soaking time is 18-36 hours.
The invention preferably adopts a freeze drying mode to dry the polyvinyl alcohol-polyaniline conductive hydrogel loaded with cobalt ions and treated by weak base. Freeze-drying helps to preserve the characteristic porous nature of the hydrogel so that, after calcination in an inert atmosphere, an elemental cobalt nanocrystalline composite is obtained that is encapsulated by a nitrogen-containing carbon material.
Wherein the calcination time is preferably 1-5 h.
More specifically, the method comprises the step of heating the cobalt ion-impregnated weak base-treated polyvinyl alcohol-polyaniline conductive hydrogel from room temperature to 300-800 ℃ at a speed of 1-5 ℃/min for calcination.
The invention adopts weak base treated polyvinyl alcohol-polyaniline conductive hydrogel as a brand new catalyst carrier, adopts a simple impregnation method to load transition metal cobalt to replace the traditional noble metal, and obtains the nitrogen-containing carbon material wrapped simple-substance cobalt nanocrystalline composite material by calcination. The cobalt-based composite catalyst used as the anode of the direct methanol fuel cell 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 Co-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 Co-N-C composite catalyst prepared by the invention is tested by adopting a cyclic voltammetry, and the peak current density of 0.6V in the mixed electrolyte of 1M potassium hydroxide and 1M methanol solution can reach 119.1mA ∙ cm under the scanning rate of 50mV/s2Has obvious catalytic effect on methanol. Meanwhile, under the voltage of 0.6V, the current density retention rate is up to 70.2 percent through a test of a timing current method i-t for 10h, and the stability is far higher than that of a commercial Pt/C electrode.
Drawings
FIG. 1 is an X-ray diffraction pattern of Co-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 10h 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.
0.0303g (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, 0.233g (2.5mmol) of Aniline (AN) and 62 mu L of deionized water into 2mL of 10wt% 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 1.375mL of 2mol/L Ammonium Persulfate (APS) solution, quickly and uniformly stirring, 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 PPH.
Soaking PPH in 1mol/L ammonia water until the film turns to dark purple, taking out, cleaning with deionized water, soaking in 1mol/L cobalt chloride solution for 24h, taking out, cleaning with deionized water, freeze drying for 10h, placing in a tubular reaction furnace, and reacting in N in a tubular reaction furnace2Raising 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 Co-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 is proved to be the simple substance cobalt by comparing the standard JCPDS card number 05-0727 with three different crystal phases of the simple substance cobalt (100), (002), (101) at the diffraction angles of 2 theta =41.7 degrees, 44.8 degrees and 47.6 degrees.
Example 2.
0.0243g (0.14mmol) 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, 0.175g (1.9mmol) of Aniline (AN) and 62 mu L of deionized water into 2mL of 10wt% 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 1.5mL of 2mol/L Ammonium Persulfate (APS) solution, quickly and uniformly stirring, 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 PPH.
Soaking PPH in 2mol/L ammonia water until the film turns to dark purple, taking out, cleaning with deionized water, soaking in 1mol/L cobalt chloride solution for 24h, taking out, cleaning with deionized water, freeze drying for 10h, and placing in a tubular reaction furnaceIn 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 Co-N-C catalyst.
Example 3.
0.0358g (0.21mmol) 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, 0.264g (2.8mmol) Aniline (AN) and 234 muL deionized water into 2mL 10wt% 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 1.652mL 2mol/L Ammonium Persulfate (APS) solution, quickly and uniformly stirring, 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 PPH.
Soaking PPH in 0.5mol/L ammonia water until the film turns to dark purple, taking out, cleaning with deionized water, soaking in 2mol/L cobalt chloride solution for 24h, taking out, cleaning with deionized water, freeze drying for 10h, placing in a tubular reaction furnace, and reacting in N in a tubular reaction furnace2Raising the temperature from room temperature to 700 ℃ 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 Co-N-C catalyst.
Example 4.
0.0182g (0.11mmol) 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, 0.189g (2.0mmol) of Aniline (AN) and 710 mu L of deionized water into 2mL of 10wt% 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 0.937mL of 2mol/L Ammonium Persulfate (APS) solution, quickly and uniformly stirring, 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 PPH.
Soaking PPH in 1mol/L ammonia water,after the film becomes dark purple, taking out the film, washing the film by deionized water, soaking the film in 0.5mol/L cobalt chloride solution for 24 hours, taking out the film, washing the film by deionized water, freeze-drying the film for 10 hours, putting the film in a tubular reaction furnace, and performing reaction in a N atmosphere2Raising the temperature from room temperature to 800 ℃ 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 Co-N-C catalyst.
Example 1 is applied.
Weighing 5mg of the Co-N-C catalyst prepared in the example 1, placing the Co-N-C catalyst in a centrifuge tube, adding 50 muL of absolute ethyl alcohol, ultrasonically dispersing for 15min, sucking 5 muL by using a pipette, uniformly dropwise adding the catalyst on the surface of hydrophilic carbon cloth with the specification of 0.5cm multiplied by 0.5cm, and drying at room temperature.
And (3) taking the carbon cloth coated with the Co-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 Co-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, in 1M potassium hydroxide solution, the scanning speed is 50mv/s, and the corresponding current density is 42.44mA ∙ cm under the voltage of 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 119.1mA ∙ cm under the voltage of 0.6V2The catalyst has obvious catalytic effect on methanol.
In FIG. 3, the current density after 10h in the mixed solution of 1M potassium hydroxide and 1M methanol was examined by the time current method i-t test of 10h, i.e. kept at 0.6V, and the result shows that the current density after 10h is still kept at 83.6mA ∙ cm-2The initial current density was (119.1 mA ∙ cm)-2) 70.2% of the total weight of the catalyst, indicating that the catalyst has better stability.
The performance index comparison of the cobalt-based catalyst reported in part of the literature is given in table 1 below. The traditional cobalt-based catalyst has expensive preparation raw materials, complex preparation method and preparation process, and low uniform dispersion degree of the active component cobalt, which directly influences the electrochemical reaction activity of methanol oxidation.
As can be seen from the data in table 1, the current density values in the cited documents are very low in both the voltage windows 1.65V and 1.46V (vs rhe), and the stability is also poor compared to the present invention, 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 cobalt 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.
Figure DEST_PATH_IMAGE001
[1] Cobalt-incorporated, nitrogen-doped carbon nanofibers as effective non-precious catalyst for methanol electrooxidation in alkaline medium, Appl. Catal., A, 498(2015), 230-240。
[2] Novel Co-MOF/Graphene Oxide Electrocatalyst for Methanol Oxidation, Electrochim. Acta, 255(2017), 195-204。
[3] Microwave-Assisted Synthesis of Co3(PO4)2 Nanospheres for Electrocatalytic Oxidation of Methanol in Alkaline Media, Catal., 7(2017)。

Claims (9)

1. A cobalt-based composite catalyst for a direct methanol fuel cell anode is a simple substance cobalt nanocrystalline composite material which is obtained by adopting weak base treated polyvinyl alcohol-polyaniline conductive hydrogel as a carrier, impregnating the carrier with soluble cobalt salt and calcining the carrier in an inert atmosphere and is wrapped by a nitrogen-containing carbon material, wherein the simple substance cobalt content is 2-6 wt%; the weak base treated polyvinyl alcohol-polyaniline conductive hydrogel is a hydrogel product obtained by taking triaminophenylboronic acid hydrochloride, aniline and polyvinyl alcohol as raw materials, carrying out polymerization reaction in an aqueous solution system containing initiator ammonium persulfate to obtain the polyvinyl alcohol-polyaniline conductive hydrogel, and then placing the polyvinyl alcohol-polyaniline conductive hydrogel in a weak base solution for soaking treatment, wherein the weak base solution is 0.5-2 mol/L ammonia water solution.
2. The preparation method of the cobalt-based composite catalyst for the direct methanol fuel cell anode, as claimed in claim 1, comprises the steps of adding hydrochloric acid solution of triaminophenylborate hydrochloride and aniline into polyvinyl alcohol aqueous solution, after dissolving uniformly, cooling to 0 ℃, dropwise adding ammonium persulfate solution, carrying out polymerization reaction to obtain polyvinyl alcohol-polyaniline conductive hydrogel, soaking in weak base solution to obtain weak base treated polyvinyl alcohol-polyaniline conductive hydrogel, taking the polyvinyl alcohol-polyaniline conductive hydrogel as a carrier, fully soaking in soluble cobalt salt solution, taking out, washing, drying, calcining at 300-800 ℃ under inert atmosphere, cooling, crushing and grinding to obtain the Co-N-C composite catalyst.
3. The preparation method according to claim 2, wherein the molar ratio of the triaminophenylboronic acid hydrochloride to the aniline is 0.01-0.1: 1, the amount of the polyvinyl alcohol is 30-600 times of the mass of the triaminophenylboronic acid hydrochloride, and the polymerization reaction time is 6-30 h.
4. The method according to claim 2, wherein the polyvinyl alcohol aqueous solution has a mass concentration of 8 to 12 wt%.
5. The preparation method of claim 2, wherein the weak base treated polyvinyl alcohol-polyaniline conductive hydrogel is soaked in 0.5-3 mol/L soluble cobalt salt solution for 18-36 h.
6. The method according to claim 2, wherein the cobalt ion-loaded weak base-treated polyvinyl alcohol-polyaniline conductive hydrogel is freeze-dried.
7. The method according to claim 2, wherein the calcination is carried out for 1 to 5 hours.
8. The preparation method according to claim 2, wherein the cobalt ion-impregnated weak base-treated polyvinyl alcohol-polyaniline conductive hydrogel is calcined by heating from room temperature to 300-800 ℃ at a rate of 1-5 ℃/min.
9. An alkaline system direct methanol fuel cell anode coated with the catalyst of claim 1.
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