CN103769223B - Polyaniline for fuel battery negative pole-tungsten carbide composite catalyst and preparation method thereof - Google Patents

Polyaniline for fuel battery negative pole-tungsten carbide composite catalyst and preparation method thereof Download PDF

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CN103769223B
CN103769223B CN201410025156.5A CN201410025156A CN103769223B CN 103769223 B CN103769223 B CN 103769223B CN 201410025156 A CN201410025156 A CN 201410025156A CN 103769223 B CN103769223 B CN 103769223B
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polyaniline
afterwards
tungsten carbide
catalyst
washing
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朱红
张硕
骆明川
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The present invention relates to a kind of polyaniline-tungsten carbide composite catalyst and preparation method thereof for fuel battery negative pole, belong to electrochemical field. This composite catalyst is made up of polyaniline and tungsten carbide particle, and its mass percent consists of: polyaniline 95-80%, tungsten carbide 5-20%. The present invention first prepares nitrogenous precursor polyaniline, then prepares this catalyst with polyaniline and tungsten carbide by high-temperature heat treatment, can control the theoretical content of tungsten carbide by this kind of method. This catalyst has higher initial hydrogen reduction current potential, is a kind of novel Proton Exchange Membrane Fuel Cells non-platinum catalyst; This catalyst preparation process is simple simultaneously, with low cost and environmentally friendly, is with a wide range of applications.

Description

Polyaniline for fuel battery negative pole-tungsten carbide composite catalyst and preparation method thereof
Technical field
The present invention relates to a kind of for fuel battery negative pole polyaniline-tungsten carbide (PANI-WC) composite catalyst andPreparation method, belongs to electrochemical field.
Background technology
Fuel cell is a kind of electrochemical appliance that directly chemical energy is transformed into electric energy, and one of its critical material is electricityElectrode catalyst, for a long time, the noble metals such as platinum, ruthenium are widely used because it has remarkable catalytic performance always.Alloy catalyst can reduce the carrying capacity of Pt, improves catalytic efficiency, but need at aspects such as catalyst stabilities to improve.Nucleocapsid catalyst, owing to having unique catalytic performance, is more and more subject to people's concern in recent years, thereby extensively shouldFor various chemical process. But Pt is expensive, scarcity of resources and easily poisoning by CO, hindered itsApplication in fuel cell. In order to accelerate the commercialization process of fuel cell, reduce the cost of fuel cell, peopleExploitation non-precious metal catalyst has been carried out to a large amount of research. Contain MN4The transition metal macrocyclic compound of structure,Owing to thering is high conjugated structure and chemical stability, hydrogen reduction is shown to good catalytic activity and stability,Become gradually in recent years the research direction of oxygen reduction catalyst, to replacing precious metals pt as fuel cell the moonUtmost point oxygen reduction catalyst.
According to current research situation, non-precious metal electrocatalyst for cathode can be divided into: transition metal macrocyclic chelateClass catalyst, metal oxide doping compound, phase transient metal sulfide and novel conductive polymer eelctro-catalyst etc.
1. transition metal macrocyclic chelate catalyst: be some macrocyclic compound that contain transition metal central atom, asContain Fe, Co, Ni, the phthalein mountain valley with clumps of trees and bamboo, porphyrin and the purine complex compound etc. of Mn, have good activity to hydrogen reduction,Research simultaneously finds that corresponding heat treatment can improve such catalyst activity and stability, and wherein N atomic molar number is4 transition-metal catalyst is considered to be hopeful to replace Pt most becomes novel fuel battery cathod catalyst.
2. blended metal oxide: Mn oxide comprises MnO, MnO2、MnOOH、Mn2O3、Mn3O4Deng, there is good hydrogen reduction catalytic activity, low price, aboundresources, have broad application prospects. PerovskiteType oxide all has good catalytic activity to hydrogen reduction and oxygen evolution reaction, has higher electron conduction, suitableThe advantages such as magnetic, resistance to oxidation, low price, become a kind of difunctional oxygen electrode catalysis material that has development prospect.
3. phase transient metal sulfide is a class non-platinum catalyst of resistance to formaldehyde that is just obtaining concern at present, and it contains central authoritiesOctahedra metal atomic cluster M6O8XX, M is high valence state transition metal, the most common with Mo; X be S, Se,The chalcogens such as Te). Conventionally by the simple substance of element at high temperature (approximately 1200 DEG C of left and right) carry out solid phase reaction and obtain,Mainly contain binary thing Mo6O8, ternary thing Mo6-xMxX8(M is the extra additional metal ion inserting) and false twoThe thing Mo of unit6-xMxX8(M is other metallic elements that replace molybdenum element) three class materials. Researcher successfully closes Co3S4Compound, the catalytic reduction activity that it has had in the sulfuric acid electrolyte of 0.5mol/L, but it is mainly by twoElectron reduction.
4. conducting polymer doping non-precious metal catalyst has obtained research widely. In this class catalyst, non-Precious metal is entrained in polymeric matrix, is conducive to catalytic activity point and disperses, thereby improve catalytic activity. MainlyThe non-precious metal material of research comprises Fe, Co, Ni and their alloy.
CN201310041096.1 discloses a kind of system of nanometer sandwich structure fuel cell non-precious metal catalystPreparation Method. This catalyst has three-dimensional manometer sandwich structure, by common group of transition metal, carbon and three kinds of elements of nitrogenBecome; Its structure is made up of graphene sheet layer and middle conductive nano carbon-coating, and transition metal and nitrogen are doped in graphiteIn the structure of alkene and conductive nano carbon, transition metal is any one or two kinds in Fe and Co. Preparation is by oxygenFunctionalized graphene, conductive nano carbon, transition metal precursor salt is dispersed in deionized water, through rotary evaporation, freezingDry, pulverize, there is 600-1000 DEG C of heat treatment in atmosphere and obtain at nitrogenous source. Advantage of the present invention: preparation sideMethod is simple, and cost is low, and the membrane electrode of being prepared by this catalyst has ordering feature, can effectively improve catalystThe physics of layer and electrochemistry are than table surface area and mass transfer ability; The Fe, the Co catalyst cheapness that use; Catalyst toolHave excellent hydrogen reduction activity, but the shortcoming of the method is the poor catalyst stability of preparation, service life is short.
Summary of the invention
Main purpose of the present invention is to provide a kind of fuel battery negative pole polyaniline-tungsten carbide compound base metalCatalyst, this catalyst has that cost is low, the feature of good stability and high catalytic activity.
A kind of polyaniline-tungsten carbide (PANI-WC) composite catalyst for fuel battery negative pole, this composite byPolyaniline is as nitrogenous precursor, and active component is made up of polyaniline and tungsten carbide particle. Its mass percent compositionFor: polyaniline: 95-80wt%, tungsten carbide: 5-20wt%.
Wherein, in above-mentioned catalyst, the particle size of polyaniline is 200-600nm, the particle size range of tungsten-carbide powder1-1.40 μ m.
Another object of the present invention is to provide the compound base metal of above-mentioned fuel battery negative pole polyaniline-tungsten carbide and urgesThe preparation method of agent.
The preparation method of one polyaniline-tungsten carbide (PANI-WC) composite catalyst for fuel battery negative pole, bagDraw together following steps:
A. in hydrochloric acid solution, add aniline, continue to stir; Ammonium persulfate is dissolved in hydrochloric acid solution, afterwards willThe ammonium persulfate solution obtaining is added drop-wise in the mixed solution of hydrochloric acid and aniline, ice bath protection, and this process continues to stir;Then add liquor natrii hypochloritis, add liquor natrii hypochloritis to stop afterwards stirring, react; After reaction finishes,Reactant is carried out to filtering and washing, first with hydrochloric acid solution washing, then with ultra-pure water washing, finally wash with acetone;Finally by dry, grind, obtain cyan polyaniline powder;
B. the polyaniline powder obtaining in step a is dispersed in ultra-pure water uniformly, adds tungsten-carbide powder, holdContinuous stirring, carries out recombination reaction; After having reacted, by reactant filtering and washing, reactant is washed with ultra-pure waterTo neutral, drying, grinds, and obtains powder;
C. the powder obtaining in step b is put into porcelain boat, porcelain boat is put into airtight tube furnace, pass into nitrogenPurge, start program heats up afterwards, is warmed up to 900-1100 DEG C and keeps 0.5-2h, cooling under nitrogen protection afterwardsTo room temperature, grind, obtain target catalyst, i.e. PNAI-WC non-precious metal catalyst.
In step a, add liquor natrii hypochloritis to stop afterwards stirring, the time of reacting is 1-24h, i.e. systemThe reaction time of standby polyaniline is 1-24h, is preferably 12-18h. The rate of addition of ammonium persulfate solution is 60-90Drip/min.
In said method, prepare the reaction equation of polyaniline:
In step b, the weight ratio of polyaniline and tungsten carbide is: (95-80): (5-20). The granularity of tungsten-carbide powderScope is 1-1.40 μ m.
Described complex reaction time is 12-15h.
In step c, the flow that passes into nitrogen is: 80-120ml/min.
Described heating rate is 5-15 DEG C/min.
The concrete steps of said method comprise:
A. get the hydrochloric acid solution of 100-150ml1mol/L in there-necked flask, add the aniline of 1.5-1.9ml, continueStir; Get the ammonium persulfate of 4.5-6.0g, be dissolved in the hydrochloric acid solution of 100-150ml1mol/L, itAfter ammonium persulfate solution is added dropwise in the there-necked flask that aniline is housed rapidly, ice bath protection, makes the temperature of this reactionRemain on below 10 DEG C, this process continues to stir, afterwards to the inferior chlorine that adds 2-5ml5wt% in there-necked flaskAcid sodium solution, adds liquor natrii hypochloritis to stop afterwards stirring, and keeps 1-24h; Afterwards reactant is carried out to suction filtrationWashing, first with the hydrochloric acid solution washing of 1-2mol/L, next with ultra-pure water washing, then with acetone washing,After in the baking oven of 80 DEG C dry 24h, grind, obtain cyan polyaniline powder;
B. the 0.4-0.6g polyaniline powder obtaining in step a is dispersed in 100-200ml ultra-pure water uniformly,Tungsten-carbide powder is added in above-mentioned solution, and the content of the tungsten carbide adding accounts for the 5-20wt% of total reactant quality,After adding tungsten-carbide powder, continue to stir; Reaction temperature is room temperature, after reaction 12-15h, stops reaction,By reactant filtering and washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 2h, obtainsPowder, grinds, stand-by;
C. the powder obtaining in step b is put into porcelain boat, porcelain boat is put into airtight tube furnace, pass into nitrogenPurge 30-60min, start program heats up afterwards, and heating rate is 5-15 DEG C/min, is warmed up to 900-1100 DEG C of guarantorHold 0.5-2h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains target catalyst,PNAI-WC non-precious metal catalyst.
Of the present invention for fuel battery negative pole polyaniline-tungsten carbide composite catalyst with polyaniline and tungsten carbide by highWarm processing is prepared from. Wherein being used for the polyaniline of Kaolinite Preparation of Catalyst can obtain by the differential responses time: poly-The reaction time of aniline is respectively 1-24h; In catalyst, the percentage composition of tungsten carbide is 5-20wt%. This catalysisAgent has higher initial hydrogen reduction current potential, is a kind of novel Proton Exchange Membrane Fuel Cells non-platinum catalyst. ShouldCatalyst is first to prepare nitrogenous precursor polyaniline, then with tungsten carbide particle carry out compound, can by this kind of methodTo control theoretically the content of tungsten carbide in catalyst. This catalyst preparation process is simple, with low cost and rightEnvironmental friendliness, is with a wide range of applications.
Brief description of the drawings
Fig. 1 is that the base metal of the different tungsten carbide content of preparation in embodiment 1,2,3,4 and comparative example 1 is urgedThe XRD spectra of agent.
The reaction time that Fig. 2-1 to Fig. 2-3 are respectively the polyaniline of preparation in embodiment 1 is 16h, tungsten carbideContent is the scanning electron microscope (SEM) photograph of the catalyst of 5wt%, transmission electron microscope and EDX spectrogram.
Fig. 3 is embodiment 1,2,3,4 and the polarization curves of oxygen reduction figure of comparative example 1.
Fig. 4 is the polarization curves of oxygen reduction figure of embodiment 1 and comparative example 2.
Fig. 5 is the polarization curves of oxygen reduction figure of the business-like JM-Pt/C catalyst of embodiment 1 and 40%.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, but do not mean that protection domain of the present inventionRestriction.
Embodiment 1:
(1) hydrochloric acid solution of getting 100ml1mol/L, in there-necked flask, adds the aniline of 1.9ml wherein, holdsContinuous stirring, gets the ammonium persulfate of 5.7g, be dissolved in the hydrochloric acid solution of 100ml1mol/L, afterwards incited somebody to actionAmmonium sulfate is added dropwise in the there-necked flask that aniline is housed rapidly, and ice bath protection, remains on the temperature of this reactionBelow 10 DEG C, this process continues to stir, afterwards to the liquor natrii hypochloritis who adds 2ml5wt% in there-necked flask,After adding sodium hydrosulfide solution, stop stirring. Reaction time is 16h. Afterwards reactant is carried out to filtering and washing,First, with the hydrochloric acid solution washing of 1mol/L, next, with ultra-pure water washing, finally wash with acetone. Finally at 80 DEG CBaking oven in dry 24h, grind, obtain cyan powder, be PANI.
(2) polyaniline powder obtaining in step (1) is dispersed in 200ml ultra-pure water uniformly to polyanilineQuality be 0.400g, get 0.021g tungsten-carbide powder and add in above-mentioned solution, it is right to add after tungsten-carbide powderThis reaction continues to stir, and the reaction temperature of this reaction is room temperature. After reaction 12h, stop reaction. By reactantFiltering and washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 24h, obtains powder, grindsMill, stand-by;
(3) powder obtaining in step (2) is put into porcelain boat, porcelain boat is put into airtight tube furnace, logicalEnter nitrogen blowing 30min, start program heats up afterwards, and heating rate is 10 DEG C/min, is warmed up to 1000 DEG C of maintenances1h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains target catalyst.
Embodiment 2:
(1) hydrochloric acid solution of getting 150ml1mol/L, in there-necked flask, adds the aniline of 1.5ml wherein, holdsContinuous stirring, gets the ammonium persulfate of 4.7g, be dissolved in the hydrochloric acid solution of 120ml1mol/L, afterwards incited somebody to actionAmmonium sulfate is added dropwise in the there-necked flask that aniline is housed rapidly, and ice bath protection, remains on the temperature of this reactionBelow 10 DEG C, this process continues to stir, afterwards to the liquor natrii hypochloritis who adds 3ml5wt% in there-necked flask,After adding sodium hydrosulfide solution, stop stirring. Reaction time is 16h. Afterwards reactant is carried out to filtering and washing,First, with the hydrochloric acid solution washing of 1mol/L, next, with ultra-pure water washing, finally wash with acetone. Finally at 80 DEG CBaking oven in dry 24h, grind, obtain cyan powder, be PANI.
(2) polyaniline powder obtaining in step (1) is dispersed in 200ml ultra-pure water uniformly to polyanilineQuality be 0.400g, get 0.044g tungsten-carbide powder and add in above-mentioned solution, it is right to add after tungsten-carbide powderThis reaction continues to stir, and the reaction temperature of this reaction is room temperature. After reaction 12h, stop reaction. By reactantFiltering and washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 24h, obtains powder, grindsMill, stand-by.
(3) powder obtaining in step (2) is put into porcelain boat, porcelain boat is put into airtight tube furnace, logicalEnter nitrogen blowing 40min, start program heats up afterwards, and heating rate is 15 DEG C/min, is warmed up to 1000 DEG C of maintenances1h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains target catalyst.
Embodiment 3:
(1) hydrochloric acid solution of getting 120ml1mol/L, in there-necked flask, adds the aniline of 1.6ml wherein, holdsContinuous stirring, gets the ammonium persulfate of 5.0g, be dissolved in the hydrochloric acid solution of 150ml1mol/L, afterwards incited somebody to actionAmmonium sulfate is added dropwise in the there-necked flask that aniline is housed rapidly, and ice bath protection, remains on the temperature of this reactionBelow 10 DEG C, this process continues to stir, afterwards to the liquor natrii hypochloritis who adds 4ml5wt% in there-necked flask,After adding sodium hydrosulfide solution, stop stirring. Reaction time is 16h. Afterwards reactant is carried out to filtering and washing,First, with the hydrochloric acid solution washing of 1.5mol/L, next, with ultra-pure water washing, finally wash with acetone. Finally existIn the baking oven of 80 DEG C, dry 24h, grinds, and obtains cyan powder, is PANI.
(2) polyaniline powder obtaining in step (1) is dispersed in 200ml ultra-pure water uniformly to polyanilineQuality be 0.400g, get 0.071g tungsten-carbide powder and add in above-mentioned solution, it is right to add after tungsten-carbide powderThis reaction continues to stir, and the reaction temperature of this reaction is room temperature. After reaction 12h, stop reaction. By reactantFiltering and washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 24h, obtains powder, grindsMill, stand-by.
(3) powder obtaining in step (2) is put into porcelain boat, porcelain boat is put into airtight tube furnace, logicalEnter nitrogen blowing 50min, start program heats up afterwards, and heating rate is 5 DEG C/min, is warmed up to 1000 DEG C of maintenances1h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains target catalyst.
Embodiment 4:
(1) hydrochloric acid solution of getting 100ml1mol/L, in there-necked flask, adds the aniline of 1.8ml wherein, holdsContinuous stirring, gets the ammonium persulfate of 5.6g, be dissolved in the hydrochloric acid solution of 150ml1mol/L, afterwards incited somebody to actionAmmonium sulfate is added dropwise in the there-necked flask that aniline is housed rapidly, and ice bath protection, remains on the temperature of this reactionBelow 10 DEG C, this process continues to stir, afterwards to the liquor natrii hypochloritis who adds 2ml5wt% in there-necked flask,After adding sodium hydrosulfide solution, stop stirring. Reaction time is 16h. Afterwards reactant is carried out to filtering and washing,First, with the hydrochloric acid solution washing of 1mol/L, next, with ultra-pure water washing, finally wash with acetone. Finally at 80 DEG CBaking oven in dry 24h, grind, obtain cyan powder, be PANI.
(2) polyaniline powder obtaining in step (1) is dispersed in 200ml ultra-pure water uniformly to polyanilineQuality be 0.400g, get 0.1g tungsten-carbide powder and add in above-mentioned solution, add after tungsten-carbide powder thisReaction continues to stir, and the reaction temperature of this reaction is room temperature. After reaction 15h, stop reaction. Reactant is taken outFilter washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 24h, obtains powder, grind,Stand-by.
(3) powder obtaining in step (2) is put into porcelain boat, porcelain boat is put into airtight tube furnace, logicalEnter nitrogen blowing 30min, start program heats up afterwards, and heating rate is 10 DEG C/min, is warmed up to 1000 DEG C of maintenances1h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains target catalyst.
Embodiment 5:
(1) hydrochloric acid solution of getting 100ml1mol/L, in there-necked flask, adds the aniline of 1.9ml wherein, holdsContinuous stirring, gets the ammonium persulfate of 5.7g, be dissolved in the hydrochloric acid solution of 100ml1mol/L, afterwards incited somebody to actionAmmonium sulfate is added dropwise in the there-necked flask that aniline is housed rapidly, and ice bath protection, remains on the temperature of this reactionBelow 10 DEG C, this process continues to stir, afterwards to the liquor natrii hypochloritis who adds 2ml5wt% in there-necked flask,After adding sodium hydrosulfide solution, stop stirring. Reaction time is 1h. Afterwards reactant is carried out to filtering and washing,First, with the hydrochloric acid solution washing of 1mol/L, next, with ultra-pure water washing, finally wash with acetone. Finally at 80 DEG CBaking oven in dry 24h, grind, obtain cyan powder, be PANI.
(2) polyaniline powder obtaining in step (1) is dispersed in 200ml ultra-pure water uniformly to polyanilineQuality be 0.400g, get 0.044g tungsten-carbide powder and add in above-mentioned solution, it is right to add after tungsten-carbide powderThis reaction continues to stir, and the reaction temperature of this reaction is room temperature. After reaction 12h, stop reaction. By reactantFiltering and washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 24h, obtains powder, grindsMill, stand-by;
(3) powder obtaining in step (2) is put into porcelain boat, porcelain boat is put into airtight tube furnace, logicalEnter nitrogen blowing 30min, start program heats up afterwards, and heating rate is 10 DEG C/min, is warmed up to 1000 DEG C of maintenances1h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains target catalyst.
Embodiment 6:
(1) hydrochloric acid solution of getting 100ml1mol/L, in there-necked flask, adds the aniline of 1.9ml wherein, holdsContinuous stirring, gets the ammonium persulfate of 5.7g, be dissolved in the hydrochloric acid solution of 100ml1mol/L, afterwards incited somebody to actionAmmonium sulfate is added dropwise in the there-necked flask that aniline is housed rapidly, and ice bath protection, remains on the temperature of this reactionBelow 10 DEG C, this process continues to stir, afterwards to the liquor natrii hypochloritis who adds 2ml5wt% in there-necked flask,After adding sodium hydrosulfide solution, stop stirring. Reaction time is 12h. Afterwards reactant is carried out to filtering and washing,First, with the hydrochloric acid solution washing of 1mol/L, next, with ultra-pure water washing, finally wash with acetone. Finally at 80 DEG CBaking oven in dry 24h, grind, obtain cyan powder, be PANI.
(2) polyaniline powder obtaining in step (1) is dispersed in 200ml ultra-pure water uniformly to polyanilineQuality be 0.400g, get 0.021g tungsten-carbide powder and add in above-mentioned solution, it is right to add after tungsten-carbide powderThis reaction continues to stir, and the reaction temperature of this reaction is room temperature. After reaction 12h, stop reaction. By reactantFiltering and washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 24h, obtains powder, grindsMill, stand-by;
(3) powder obtaining in step (2) is put into porcelain boat, porcelain boat is put into airtight tube furnace, logicalEnter nitrogen blowing 30min, start program heats up afterwards, and heating rate is 10 DEG C/min, is warmed up to 1000 DEG C of maintenances1h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains target catalyst.
Embodiment 7:
(1) hydrochloric acid solution of getting 100ml1mol/L, in there-necked flask, adds the aniline of 1.9ml wherein, holdsContinuous stirring, gets the ammonium persulfate of 5.7g, be dissolved in the hydrochloric acid solution of 100ml1mol/L, afterwards incited somebody to actionAmmonium sulfate is added dropwise in the there-necked flask that aniline is housed rapidly, and ice bath protection, remains on the temperature of this reactionBelow 10 DEG C, this process continues to stir, afterwards to the liquor natrii hypochloritis who adds 2ml5wt% in there-necked flask,After adding sodium hydrosulfide solution, stop stirring. Reaction time is 18h. Afterwards reactant is carried out to filtering and washing,First, with the hydrochloric acid solution washing of 1mol/L, next, with ultra-pure water washing, finally wash with acetone. Finally at 80 DEG CBaking oven in dry 24h, grind, obtain cyan powder, be PANI.
(2) polyaniline powder obtaining in step (1) is dispersed in 200ml ultra-pure water uniformly to polyanilineQuality be 0.400g, get 0.021g tungsten-carbide powder and add in above-mentioned solution, it is right to add after tungsten-carbide powderThis reaction continues to stir, and the reaction temperature of this reaction is room temperature. After reaction 12h, stop reaction. By reactantFiltering and washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 24h, obtains powder, grindsMill, stand-by;
(3) powder obtaining in step (2) is put into porcelain boat, porcelain boat is put into airtight tube furnace, logicalEnter nitrogen blowing 30min, start program heats up afterwards, and heating rate is 10 DEG C/min, is warmed up to 1000 DEG C of maintenances1h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains target catalyst.
Embodiment 8:
(1) hydrochloric acid solution of getting 100ml1mol/L, in there-necked flask, adds the aniline of 1.9ml wherein, holdsContinuous stirring, gets the ammonium persulfate of 5.7g, be dissolved in the hydrochloric acid solution of 100ml1mol/L, afterwards incited somebody to actionAmmonium sulfate is added dropwise in the there-necked flask that aniline is housed rapidly, and ice bath protection, remains on the temperature of this reactionBelow 10 DEG C, this process continues to stir, afterwards to the liquor natrii hypochloritis who adds 2ml5wt% in there-necked flask,After adding sodium hydrosulfide solution, stop stirring. Reaction time is 24h. Afterwards reactant is carried out to filtering and washing,First, with the hydrochloric acid solution washing of 1mol/L, next, with ultra-pure water washing, finally wash with acetone. Finally at 80 DEG CBaking oven in dry 24h, grind, obtain cyan powder, be PANI.
(2) polyaniline powder obtaining in step (1) is dispersed in 200ml ultra-pure water uniformly to polyanilineQuality be 0.400g, get 0.021g tungsten-carbide powder and add in above-mentioned solution, it is right to add after tungsten-carbide powderThis reaction continues to stir, and the reaction temperature of this reaction is room temperature. After reaction 12h, stop reaction. By reactantFiltering and washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 24h, obtains powder, grindsMill, stand-by;
(3) powder obtaining in step (2) is put into porcelain boat, porcelain boat is put into airtight tube furnace, logicalEnter nitrogen blowing 30min, start program heats up afterwards, and heating rate is 10 DEG C/min, is warmed up to 1000 DEG C of maintenances1h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains target catalyst.
Comparative example 1:
(1) hydrochloric acid solution of getting 100ml1mol/L, in there-necked flask, adds the aniline of 1.9ml wherein, holdsContinuous stirring, gets the ammonium persulfate of 5.7g, be dissolved in the hydrochloric acid solution of 100ml1mol/L, afterwards incited somebody to actionAmmonium sulfate is added dropwise in the there-necked flask that aniline is housed rapidly, and ice bath protection, remains on the temperature of this reactionBelow 10 DEG C, this process continue stir, in there-necked flask, add 2ml(5wt% afterwards) cloroxSolution, adds sodium hydrosulfide solution to stop afterwards stirring. Reaction time is 16h. Afterwards reactant is carried out to suction filtrationWashing, first, with the hydrochloric acid solution washing of 1mol/L, next, with ultra-pure water washing, finally washs with acetone. ?After in the baking oven of 80 DEG C dry 24h, grind, obtain cyan powder, be PANI.
(2) PANI being prepared by 0.4g step (1) is dissolved in 200ml ultra-pure water, stirs and is disperseed allEven, its reaction temperature is room temperature, continue stir 12h, suction filtration is isolated, with ultra-pure water wash to neutrality,Put into the dry 24h of baking oven of 80 DEG C, grind, the powder that obtains black is stand-by.
(3) powder obtaining in step (2) is put into porcelain boat, porcelain boat is put into airtight tube furnace, logicalEnter nitrogen blowing 30min, start program heats up afterwards, and heating rate is 10 DEG C/min, is warmed up to 1000 DEG C of maintenances1h, cool to room temperature under nitrogen protection afterwards, takes out sample, grinds, and obtains catalyst.
Comparative example 2:
Get the H of 100ml0.5mol/L2SO4Solution, in there-necked flask, adds the aniline of 4ml wherein, stirsMix it is fully disperseed, add afterwards the WC of 0.9g, the ammonium persulfate of getting 12.5g is dissolved in 100ml0.5The H of mol/L2SO4In solution, ammonium persulfate solution is joined in there-necked flask, ice bath protection, makes reaction systemTemperature remain on below 10 DEG C, stir, reaction 12h, polyaniline is covered on tungsten carbide particle fully,Afterwards reactant is carried out to suction filtration separation, is washed to neutral with ultra-pure water, dry grind stand-by. By what obtainPowder is put into porcelain boat, puts it in airtight tube furnace, passes into nitrogen blowing 30min, starts afterwards journeyOrder heats up, and heating rate is 10 DEG C/min, is warmed up to 1000 DEG C and keeps 1h, is cooled to afterwards under nitrogen protectionRoom temperature, takes out sample, grinds, and obtains catalyst.
The catalyst that embodiment 1-8 and comparative example 1-2 are obtained is tested as follows:
1, XRD spectra
As shown in Figure 1, be PANI-WC-0 prepared by comparative example 1 and embodiment 1-4, PANI-WC-5,PANI-WC-10, PANI-WC-15, the XRD spectra of five kinds of catalyst of PANI-WC-20. In five curves,(a) be the XRD figure of the content of the WC catalyst that is 0,2 θ=25 ° and 43 ° are located as C(002) and (101)Diffraction, expression be the carbon of the nitrogen retention of part graphite-structure; (b) (c) (d) (e) curve be respectively PANI-WC-5,PANI-WC-10, PANI-WC-15, the XRD spectra of PANI-WC-20 catalyst, the diffraction occurring in spectrogramPeak judges it is the diffraction maximum of WC according to (JCPDSNo.51-0939), and therefore in catalyst, W is with carbonThe form of changing tungsten exists.
2, ESEM, transmission electron microscope and EDX(energy dispersion x-ray spectrometer) spectrogram
As shown in Figure 2, the ESEM of the PANI-WC-5 catalyst of preparing for embodiment 1, transmission electron microscope withAnd EDX spectrogram. From Fig. 2-1, can find out that the catalyst after high-temperature heat treatment presents graininess, has largerSpecific area, from Fig. 2-2, can find out, the catalyst of preparing presents the structure of nitrogen cladded wolfram carbide,From the EDX spectrogram of Fig. 2-3, can find out the existence that has W elements in catalyst, in conjunction with XRD spectra, canDetermine that in catalyst, tungsten is to exist with the formation of tungsten carbide.
3, LSV(hydrogen reduction polarization) curve
As shown in Figure 3, be PANI-WC-0 prepared by comparative example 1 and embodiment 1-4, PANI-WC-5,PANI-WC-10, PANI-WC-15, the LSV curve of five kinds of catalyst of PANI-WC-20. Embodiment 1 is to realityExecuting example 4 is to add the catalyst of preparing after tungsten carbide. As can be seen from Figure 3, curve (b), (c), (d),(e) all high than the initial reduction potential of oxygen of curve (a). In tungsten carbide, carbon atom will be contributed theoreticallyOuter field four electronics are to W elements (W, 4f145d46s2) d atom, and move to right four in its periodic table of elementsColumn position elements platinum (Pt, 4f145d96s1) identical, final effect is after carbonization is closed, the characteristic electron of tungsten more connectsBe bordering on platinum group metal, cause the catalytic performance of tungsten carbide similar to platinum group metal. From figure, it can also be seen that embodiment2 catalyst of preparing have best initial reduction potential, are 0.85V, now the reason of tungsten carbide in catalystOpinion content is 5wt%, illustrates and has good electrocatalytic properties with the prepared catalyst of embodiment 2 methods, withIt is best that other compare catalytic performance.
To embodiment 5, embodiment 6, embodiment 2, embodiment 7, the catalyst that embodiment 8 prepares also does oxygenFormer polarization curve test, can find out from test result, polymerization time is 1h, 12h, 16h, 18h and 24hThe initial reduction potential of oxygen of the catalyst prepared of polyaniline be respectively 0.78V, 0.79V, 0.80V, 0.78VAnd 0.76V, therefore the polymerization time of polyaniline is that the catalyst that 16h prepares has the initial reduction electricity of the highest oxygenPosition.
As shown in Figure 4, be the LSV curve of the prepared catalyst of embodiment 1 and comparative example 2, be (a) rightThe polarization curves of oxygen reduction of ratio 2, (b) is the polarization curves of oxygen reduction of embodiment 1, as can be seen from the figure,Comparative example 2 has very low initial reduction potential.
As shown in Figure 5, be the LSV curve of embodiment 1 and 40% business-like JM-Pt/C catalyst. From curveIn can find out that embodiment 1 is compared with business-like JM-Pt/C catalyst, the low 0.1V of initial reduction potential, explanationIt has with business-like JM-Pt/C catalyst and has suitable catalytic activity.

Claims (7)

1. the preparation method of the composite catalyst of polyaniline-tungsten carbide for fuel battery negative pole, it is characterized in that: polyaniline for described fuel battery negative pole-tungsten carbide composite catalyst is made up of polyaniline and tungsten carbide particle, its mass percent consists of: polyaniline 95-80%, tungsten carbide 5-20%;
Comprise the steps:
A. in hydrochloric acid solution, add aniline, continue to stir; Ammonium persulfate is dissolved in hydrochloric acid solution, afterwards the ammonium persulfate solution obtaining is added drop-wise in the mixed solution of hydrochloric acid and aniline, ice bath protection, this process continues to stir; Then add liquor natrii hypochloritis, add liquor natrii hypochloritis to stop afterwards stirring, react; After reaction finishes, reactant is carried out to filtering and washing, first with hydrochloric acid solution washing, then with ultra-pure water washing, finally wash with acetone; Finally by dry, grind, obtain cyan polyaniline powder;
B. the polyaniline powder obtaining is dispersed in ultra-pure water uniformly, adds tungsten-carbide powder, continue to stir, carry out recombination reaction; After having reacted, by reactant filtering and washing, with ultra-pure water, reactant washing is extremely neutral, drying, grinds, and obtains powder;
C. the powder obtaining is put into porcelain boat, porcelain boat is put into airtight tube furnace, pass into nitrogen blowing, start program heats up afterwards, is warmed up to 900-1100 DEG C and keeps 0.5-2h, and cool to room temperature under nitrogen protection afterwards, grinds, and obtains target catalyst.
2. the preparation method of polyaniline-tungsten carbide composite catalyst for fuel battery negative pole according to claim 1, is characterized in that: after adding liquor natrii hypochloritis, stop stirring, the time of reacting is 1-24h.
3. the preparation method of polyaniline-tungsten carbide composite catalyst for fuel battery negative pole according to claim 2, is characterized in that: after adding liquor natrii hypochloritis, stop stirring, the time of reacting is 12-18h.
4. the preparation method of polyaniline-tungsten carbide composite catalyst for fuel battery negative pole according to claim 1, is characterized in that: the rate of addition of ammonium persulfate solution is drip/min of 60-80.
5. the preparation method of polyaniline-tungsten carbide composite catalyst for fuel battery negative pole according to claim 1, is characterized in that: described complex reaction time is 12-15h.
6. the preparation method of polyaniline-tungsten carbide composite catalyst for fuel battery negative pole according to claim 1, is characterized in that: the flow that passes into nitrogen is: 30-60ml/min, described heating rate is 5-15 DEG C/min.
7. the preparation method of polyaniline-tungsten carbide composite catalyst for fuel battery negative pole according to claim 1, is characterized in that, comprises following concrete steps:
A. get the hydrochloric acid solution of 100-150ml1mol/L in there-necked flask, add the aniline of 1.5-1.9ml, continue to stir; Get the ammonium persulfate of 4.5-6.0g, be dissolved in the hydrochloric acid solution of 100-150ml1mol/L, afterwards ammonium persulfate solution is added dropwise in the there-necked flask that aniline is housed, ice bath protection, the temperature of this reaction is remained on below 10 DEG C, and this process continues to stir, afterwards to the liquor natrii hypochloritis who adds 2-5ml5wt% in there-necked flask, after adding liquor natrii hypochloritis, stop stirring, keep 1-24h; Afterwards reactant is carried out to filtering and washing, first use the hydrochloric acid solution washing of 1-2mol/L, next with ultra-pure water washing, then with acetone washing, finally in the baking oven of 80 DEG C, be dried 24h, grind, obtain cyan polyaniline powder;
B. the 0.3-0.5g polyaniline powder obtaining is dispersed in 100-200ml ultra-pure water uniformly, tungsten-carbide powder is added in above-mentioned solution, the content of the tungsten carbide adding accounts for the 5-20wt% of total reactant quality, adds tungsten-carbide powder to continue afterwards to stir; Reaction temperature is room temperature, after reaction 12-15h, stops reaction, and by reactant filtering and washing, with ultra-pure water, reactant washing is extremely neutral, in 80 DEG C of baking ovens, dry 24h, obtains powder, grinds, stand-by;
C. the powder obtaining is put into porcelain boat; porcelain boat is put into airtight tube furnace; pass into nitrogen blowing 30-60min; start program heats up afterwards, and heating rate is 5-15 DEG C/min, is warmed up to 900-1100 DEG C and keeps 0.5-2h; cool to room temperature under nitrogen protection afterwards; take out sample, grind, obtain target catalyst.
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A novel non-precious metal catalyst synthesized via pyrolysis of polyaniline-coated tungsten carbide particles for oxygen reduction reaction;Kezhu Jiang et al.;《Journal of Power Sources》;20120802;第219卷;第250页第2节以及第252页第4节 *
Polyaniline/mesoporous tungsten trioxide composite as anode electrocatalyst for high-performance microbial fuel cells;Yaqiong Wang et al.;《Biosensors and Bioelectronics》;20121004;第41卷;第583页第2节 *
合成聚苯胺/碳化钨复合材料及聚合机理探讨;黄惠等;《高分子学报》;20101031(第10期);第1180页第1节 *
聚合物膜燃料电池阴极非Pt 催化剂;赵东江等;《化学进展》;20091231;第21卷(第12期);第2754页第1-5节 *

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