CN101716504B - Preparation method of conducting polymer modified carbon-supported manganese-based compound catalyst - Google Patents
Preparation method of conducting polymer modified carbon-supported manganese-based compound catalyst Download PDFInfo
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- CN101716504B CN101716504B CN200910154902XA CN200910154902A CN101716504B CN 101716504 B CN101716504 B CN 101716504B CN 200910154902X A CN200910154902X A CN 200910154902XA CN 200910154902 A CN200910154902 A CN 200910154902A CN 101716504 B CN101716504 B CN 101716504B
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Abstract
The invention relates to the fields of batteries and air batteries, and aims to provide a preparation method of a conducting polymer modified carbon-supported manganese-based compound catalyst for oxygen electrochemical reduction. The preparation method comprises the following steps of: dispersing a carbon material into a solvent to prepare a suspension, adding glacial acetic acid or hydrochloric acid to regulate a pH value, and stirring at room temperature; adding pyrrole or thiofuran, and stirring; then adding anhydrous MnCl2 as a metal source of a catalyst, adding H2O2 as an initiator of polyreaction, stirring and microwave heating by microwave; then adding an alkaline sodium borohydride solution as a reducing agent, stirring, microwave heating by microwave and naturally cooling; washing with deionized water, filtering and vacuum drying; and preserving heat for one hour under an inert atmosphere for heat treatment. The invention adopts a one-step method for synthesizing the compound catalyst, and the synthesizing process is simple and convenient. Catalyst particles with uniform size and homogeneous distribution can be obtained through the adoption of microwave heating, and the synthesizing time of the catalyst is shortened. Mn at a catalytic site can be directly bonded with C through the heat treatment, and the activity and the stability of the catalyst are improved.
Description
Technical field
The present invention relates to fuel cell and air cell field, specifically, is a kind of battery and air cell cathod catalyst of acting as a fuel, and is used for conducting polymer modified carbon-supported manganese-based compound catalyst of oxygen electrochemical reduction and preparation method thereof.
Background technology
Fuel cell is the energy conversion device that a kind of chemical energy that directly will be stored in the fuel changes electric energy into, because it need not through Carnot cycle, energy density and energy conversion efficiency are high, is a kind of novel green energy resource technology.In recent years, break through because the technology of fuel cell (Fuel Cell) obtains innovation, and added multiple pressures such as environmental issue and energy deficiency and arrive in succession, industries such as national governments and automobile, electric power, the energy are paid attention to the development of fuel cell technology gradually.Fuel cell is the new generation technology of high efficiency, low pollution, the diversification energy.Fuel cell uses fuel such as alcohols, natural gas, hydrogen, sodium borohydride, hydrazine to convert electric current to, makes it can continue to produce electric power, does not need the program that discharges and recharges of secondary cell.During charging, as long as refill into fuel.Fuel cell briefly is exactly a generator.Fuel cell is firepower, waterpower, outer the 4th kind of electricity-generating method of nuclear energy.
Along with the development of nanosecond science and technology, fuel cell has had proton exchange model (the proton exchange membrane fuel cell of great breakthrough, particularly low-temperature operation technically; PEMFC) appearance makes fuel cell be able to get into the category that the people's livelihood is used by unattainable space technological applications field, and PEMFC extensively is much accounted of one of the focus development technology that forms.Wherein, Adopting PEM is electrolytical direct fuel liquid battery (DLFC); Except having advantages such as the high and low discharging of the common energy conversion efficiency of other fuel cells, pollution-free and noiselessness, also have original advantage in addition: normal temperature uses, simple in structure, fuel carries that supply is convenient, a little less than volume and weight specific energy density height and the infrared signal.Especially be fit to do small-sized moving and compact power, splendid potential application foreground arranged at aspects such as national defence, communication, electric motor cars.
Usually low-temperature fuel cell need be catalyst with the precious metal material all.For reducing the cost of catalyst, mainly organize work from following two aspects: a. improves the utilization rate of platinum, reduces its consumption; B. seek the lower non-precious metal catalyst of new price.In order to reduce electrode platinum consumption, electrode all need not pure platinum, is the carbon supported platinum catalyst of preparing carriers high dispersive with the high-ratio surface carbon black, increases the surface area of platinum, improves the utilization rate of platinum.U.S. scientist has invented a kind of novel hydrogen fuel cell catalyst in the recent period, and the polypyrrole cobalt uses in the hetero atom of the non-precious metal embedding cheaply polymer architecture and processes.In the test,, in reaching 100 hours test, shown good stability though the activity that the electric energy of this catalyst produces is lower than the PEMFC catalyst based on platinum.At present the research of low-cost catalyst is mainly concentrated on macrocyclic compound catalyst and the metal carbide catalyst that transition metal atoms cluster compound catalyst, center contain transition metal; Nitride, sulfide, boride and silicide etc. also have report as the low-temperature fuel cell catalyst in addition, but the performance of these catalyst is poor, studies also fewer.
Air cell is to be that negative pole, airborne oxygen are as a kind of high-performance of positive active material, free of contamination electrochmical power source with metallic zinc, magnesium.The major technique characteristic of this product: the one, capacity is big, in light weight, specific energy is high, is 8-20 times of energy density of lead-acid accumulator.Magnesium has the electrochemical equivalent higher than zinc, but the magnesium air cell has the specific energy height, safe and convenient to use, raw material source is abundant, cost is low, fuel is easy to storing serviceability temperature wide ranges (20 ℃～80 ℃) and pollute characteristics such as little.As a kind of high-energy chemistry power supply, aspects such as instrument power source, stand-by power supply and electric automobile have broad application prospects under mobile electronic equipment power supply, autonomous type submerge device power supply, ocean water.Air cell is with KOH solution or NH
4Cl solution is made electrolyte.When being electrolyte with KOH solution, its basic functional principle is zinc or the OH in magnesium and the electrolyte on the GND (anode)
-Electrochemical reaction (anode reaction) takes place, and discharges electronics.Catalyst in the air negative reaction layer contacts with the airborne oxygen that electrolyte reaches via diffusion entering battery simultaneously, absorbs electronics, and electrochemical reaction (cathode reaction) takes place.In order to improve the performance of air cell, usually also need be with precious metal material as catalyst.
At disclosed Chinese invention patent " preparation method of conducting polymer modified carbon based cobaltous hydroxide composite catalyst " (application number: 200910098411.8; Publication number: proposed CN101549304) to prepare conducting polymer modified carbon based cobaltous hydroxide: prepare conducting polymer modified carbon black earlier, on conducting polymer modified carbon black, support cobalt hydroxide then with two-step method.Not only process is loaded down with trivial details for this method, generated time is long, causes the inactivation of conducting polymer modified layer easily, thereby causes skewness when causing supporting cobalt hydroxide, and the catalyst particle size is uneven, the problem that catalytic performance descends.And catalyst just adsorbs conducting polymer modified laminar surface, adhesion a little less than, thereby stability is relatively poor.In addition, cobalt is a strategic material, and is relatively more expensive.
Summary of the invention
The technical problem that the present invention will solve provides a kind of preparation method who is used for the conducting polymer modified carbon-supported manganese-based compound catalyst of fuel cell and air cell negative electrode.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts comprises the steps:
Material with carbon element is distributed in water, methyl alcohol, ethanol or the chloroform is made into suspension, the mass ratio of material with carbon element and solvent is 1: 10～1: 30; Adding glacial acetic acid or salt acid for adjusting pH value is 2～3, stirring at room 20～60min; Add pyrroles or thiophene again and stir 10～20min, wherein the mass ratio of pyrroles or thiophene and material with carbon element is 1: 5～1: 1; Add anhydrous MnCl then
2As the source metal of catalyst, wherein anhydrous MnCl
2With the mass ratio of material with carbon element be 1: 1～1: 10; And adding H
2O
2As initiator of polyreaction, stir and with 200W heating using microwave 1～30min, pyrroles or thiophene and H
2O
2Mass ratio be 1: 0.05～0.5; Add reducing agent alkalescence sodium borohydride solution then, make sodium borohydride and anhydrous MnCl
2The molal weight ratio be 1: 1～4: 1, stir and, cool off naturally with 500W heating using microwave 1～20min; After spending the deionised water filtration, 80～90 ℃ of drying 3～4h of vacuum; At Ar or N
2Inert atmosphere under 300～800 ℃ the insulation 1h heat-treat, make conducting polymer modified carbon-supported manganese-based compound catalyst.
As a kind of improvement, said material with carbon element is that conductive acetylene is black, in spherical carbon black or the CNT any one.
As a kind of improvement, in the final synthetic product of conducting polymer modified carbon-supported manganese-based compound catalyst, manganese-based compound is Mn, MnO, MnO
2, MnOOH or Mn (OH)
2In at least two kinds of formed compounds.
The invention has the beneficial effects as follows:
(1) adopt the synthetic composite catalyst of one-step method, synthesis technique is easy.
(2) adopt heating using microwave, the catalyst particle that not only can obtain consistent size, is evenly distributed also can shorten the catalyst generated time greatly.
(3) heat-treat can make catalytic sites Mn directly with C bonding, increase activity of such catalysts and stability.
(4) synthetic conducting polymer modified carbon-supported manganese-based compound catalyst is a non-platinum catalyst, and it is with low cost, helps popularizing of fuel cell and air cell technology, improves the performance of air cell.
Description of drawings
Fig. 1 is for using direct hydrazine fuel cell the power generation performance 10,20 ℃ under of the spherical graphite supported manganese-based compound of polypyrrole modifying as the cathode and anode catalyst;
Fig. 2 is 100 and 200mA cm as the zinc-air battery of cathod catalyst at discharge current density for using polypyrrole modifying CNT supported manganese-based compound
-2The time change in voltage.
The specific embodiment
Below in conjunction with the specific embodiment the present invention is described in further detail:
Embodiment 1:
10g spherical graphite BP 2000 is added 100g water be made into suspension, adding glacial acetic acid adjusting pH value is 2, stirring at room 20min.Add the 2g pyrrole monomer again and stir 10min, add the anhydrous MnCl of 1g afterwards
2, add the H that 2g concentration is 5wt% then
2O
2Solution is as initiator of polyreaction, stirs and with 200W heating using microwave 1min.After adding 300g alkalescence sodium borohydride solution, wherein sodium borohydride and anhydrous MnCl
2Mass ratio be 1: 1, stir and 500W heating using microwave 1min, cooling naturally, spend the deionised water filtration after, 90 ℃ of dry 3h of vacuum.300 ℃ of insulation 1h heat-treat under Ar atmosphere, make conducting polymer modified carbon-supported manganese-based compound catalyst, contain Mn (OH) in the catalyst
2And MnOOH.
Spherical graphite supported manganese-based compound 1 gram with above-mentioned polypyrrole modifying; Water; Ptfe emulsion and absolute ethyl alcohol were according to 1: 3: 7: 3 mass ratio hybrid modulation form slurry; Be coated in equably then on 80 square centimeters of carbon papers after hydrophobic is handled, behind the heat treatment 10min, naturally cool to room temperature preparation and become anodal (negative electrode) under 350 ℃ of blanket of nitrogen.Get spherical graphite supported manganese-based compound 1 gram of above-mentioned polypyrrole modifying; With catalyst; Water; Nafion solution and absolute ethyl alcohol are catalyst by mass ratio: water: Nafion solution: absolute ethyl alcohol is 1: 3: 7: 3 hybrid modulation form slurry, be coated to equably then on 80 square centimeters the nickel foam, and be prepared into negative pole (anode) after drying naturally.
To contain 10wt.%N
2H
4, the alkaline hydrazine solution of 10wt.%NaOH is fuel, oxygen is oxidant.With Nafion 117 films is electrolyte, and being assembled into response area with prepared positive pole and negative pole is 80 square centimeters direct hydrazine fuel cell, and the power generation performance of battery under 10,20 ℃ is as shown in Figure 1.
Embodiment 2:
The 10g CNT is added 150g ethanol be made into suspension, adding glacial acetic acid adjusting pH value is 2.5, stirring at room 30min.Add the 10g pyrrole monomer again and stir 15min, add the anhydrous MnCl of 2g afterwards
2, add the H that 10g concentration is 5wt% then
2O
2Solution is as initiator of polyreaction, stirs and with 200W heating using microwave 10min.After adding 300g alkalescence sodium borohydride solution, wherein sodium borohydride and anhydrous MnCl
2Mass ratio be 1.5: 1, stir and 500W heating using microwave 5min, cooling naturally, spend the deionised water filtration after, 80 ℃ of dry 4h of vacuum.300 ℃ of insulation 1h heat-treat under blanket of nitrogen, make conducting polymer modified CNT supported manganese-based compound catalyst, contain Mn (OH) in the catalyst
2And MnOOH.
With the polytetrafluoroethylene (PTFE) suspension of polypyrrole modifying CNT supported manganese-based compound catalyst, water, 5wt.% and absolute ethyl alcohol according to 1: 3: 2: 3 mass ratio hybrid modulation form slurry; Be coated on the carbon paper that hydrophobic is handled; Naturally dry back 300 ℃ of insulation 1h under the Ar inert atmosphere and heat-treat, make positive pole.
With zinc powder, spherical graphite BP 2000 and binding agent carboxymethylcellulose sodium solution (5wt.%), be modulated into slurry coating in nickel foam in 1: 0.1: 1 ratio of mass ratio, compression moulding after the drying at room temperature obtains the negative pole (anode) of zinc-air battery.The mass ratio of zinc and nickel foam is 1: 0.2.
Selecting concentration is 1mol L
-1Aqueous ammonium chloride solution as electrolyte, by anion-exchange membrane positive pole and negative pole are separated, constitute zinc-air battery, its maximum power density at room temperature can reach 150mW/cm
2Fig. 2 for air cell discharge current density be 100 with 200mA cm
-2The time performance.
Embodiment 3:
The 10g CNT is distributed in the 200g methyl alcohol is made into suspension; Adding the salt acid for adjusting pH value is 3, at stirring at room 40min; Add the 2g pyrrole monomer, stirring at room 15min.Add the anhydrous MnCl of 10g afterwards
2, add the H that 20g concentration is 5wt% then
2O
2Solution is as initiator of polyreaction, stirs and with 200W heating using microwave 30min.After slowly adding 600g alkalescence sodium borohydride solution, wherein sodium borohydride and anhydrous MnCl
2Mass ratio be 1: 4, stir and 500W heating using microwave 10min, cooling naturally, spend the deionised water filtration after, 90 ℃ of dry 4h of vacuum.Inert atmosphere N
2After following 800 ℃ of insulation 1h heat-treat drying, obtain the CNT carried nickel-based compound catalyst of polypyrrole modifying,, contain MnO, MnO in the catalyst through XRD determining
2And manganese metal.
Embodiment 4:
The 10g spherical graphite is added the 250g chloroform be made into suspension, adding the salt acid for adjusting pH value is 3, at stirring at room 60min; Add the 10g thiophene monomer, stirring at room 20min slowly adds the anhydrous MnCl of 2g afterwards
2, add the H that 20g concentration is 5wt% then
2O
2Solution is as initiator of polyreaction, stirs and with 200W heating using microwave 20min.After slowly adding 450g alkalescence sodium borohydride solution, wherein sodium borohydride and anhydrous MnCl
2Mass ratio be 1: 1.5, stir and 500W heating using microwave 20min, cool off naturally, behind the filtration washing, 80 ℃ of dry 3.5h of vacuum.Inert atmosphere N
2After insulation 1h heat-treats drying under following 600 ℃, obtain the spherical graphite supported manganese-based compound catalyst that polythiophene is modified.Through XRD determining, contain MnO in the catalyst
2, MnOOH.
Positive pole according to the preparation of the method described in the embodiment 1.Selecting concentration is 1mol L
-1The KOH aqueous solution as electrolyte. with magnesium dust, carbon black and binding agent carboxymethylcellulose sodium solution (5wt.%); Be modulated into slurry coating in nickel foam in 1: 0.1: 1 ratio of mass ratio; Compression moulding after the drying at room temperature obtains the anode of magnesium air cell.The mass ratio of magnesium and nickel foam is 1: 0.2.The nonwoven of being processed by polypropylene fibre separates positive pole and negative pole, constitutes the magnesium air cell, and its maximum power density at room temperature can reach 150mW/cm
2
Embodiment 5:
The black 300g methyl alcohol that adds of 10g conductive acetylene is made into suspension, and adding glacial acetic acid adjusting pH value is 2.5, stirring at room 30min.Add the 3g pyrrole monomer again and stir 10min, add the anhydrous MnCl of 1g afterwards
2, add the H that 5g concentration is 5wt% then
2O
2Solution is as initiator of polyreaction, stirs and with 200W heating using microwave 20min.After slowly adding 300g alkalescence sodium borohydride solution, wherein sodium borohydride and anhydrous MnCl
2Mass ratio be 1: 1, stir and 500W heating using microwave 15min, cooling naturally, spend the deionised water filtration after, 90 ℃ of dry 4h of vacuum.Inert atmosphere N
2After following 300 ℃ of insulation 1h heat-treated drying, the molar content that obtains the N atom was 0.6%, and the molar content of Mn atom is 0.3% cathod catalyst.Through XRD determining, contain Mn (OH) in the catalyst
2, MnOOH.
What more than announce at last, only is specific embodiment of the present invention.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (3)
1. the preparation method of a conducting polymer modified carbon-supported manganese-based compound catalyst may further comprise the steps:
Material with carbon element is distributed in water, methyl alcohol, ethanol or the chloroform is made into suspension, the mass ratio of material with carbon element and solvent is 1: 10～1: 30; Adding glacial acetic acid or salt acid for adjusting pH value is 2～3, stirring at room 20～60min; Add pyrroles or thiophene again and stir 10～20min, wherein the mass ratio of pyrroles or thiophene and material with carbon element is 1: 5～1: 1; Add anhydrous MnCl then
2As the source metal of catalyst, wherein anhydrous MnCl
2With the mass ratio of material with carbon element be 1: 1～1: 10; And adding H
2O
2As initiator of polyreaction, stir and with 200W heating using microwave 1～30min, pyrroles or thiophene and H
2O
2Mass ratio be 1: 0.05～0.5; Add reducing agent alkalescence sodium borohydride solution then, make sodium borohydride and anhydrous MnCl
2Mass ratio be 1: 1～4: 1, stir and, cool off naturally with 500W heating using microwave 1～20min; After spending the deionised water filtration, 80～90 ℃ of drying 3～4h of vacuum; At Ar or N
2Inert atmosphere under 300～800 ℃ the insulation 1h heat-treat, make conducting polymer modified carbon-supported manganese-based compound catalyst.
2. the preparation method of conducting polymer modified carbon-supported manganese-based compound catalyst according to claim 1 is characterized in that, said material with carbon element is that conductive acetylene is black, in spherical carbon black or the CNT any one.
3. according to the preparation method of the said conducting polymer modified carbon-supported manganese-based compound catalyst of claim 1, it is characterized in that in the conducting polymer modified carbon-supported manganese-based compound catalyst that makes according to said method, manganese-based compound is Mn, MnO, MnO
2, MnOOH or Mn (OH)
2In at least two kinds of formed compounds.
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| CN102861571A (en) * | 2012-09-10 | 2013-01-09 | 杭州电子科技大学 | Preparation method for crystal form-controllable oxygen reduction electrochemical catalyst |
| CN103212421A (en) * | 2013-03-01 | 2013-07-24 | 北京化工大学常州先进材料研究院 | Preparation method of nano-grade electro-catalyst based on graphene |
| CN103341367B (en) * | 2013-07-15 | 2014-10-15 | 上海交通大学 | Method for synthesizing carbon-supported cobalt polypyrrole oxygen reduction catalyst by alternating current one-step method |
| CN105406072B (en) * | 2015-12-09 | 2017-12-15 | 河北飞豹新能源科技有限公司 | A kind of battery of electrode overlay film |
| CN113745537B (en) * | 2021-08-27 | 2023-04-07 | 西安交通大学 | Aluminum air battery air cathode and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040253386A1 (en) * | 2003-06-13 | 2004-12-16 | Sarojini Deevi | Preparation of intermetallics by metallo-organic decomposition |
| CN101552345A (en) * | 2009-05-07 | 2009-10-07 | 浙江大学 | Fuel cell using conductive polymer modified carbon based cobaltous hydroxide composite catalyst |
| CN101549304A (en) * | 2009-05-07 | 2009-10-07 | 浙江大学 | Method for preparing conductive polymer modified carbon based cobaltous hydroxide composite catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040253386A1 (en) * | 2003-06-13 | 2004-12-16 | Sarojini Deevi | Preparation of intermetallics by metallo-organic decomposition |
| CN101552345A (en) * | 2009-05-07 | 2009-10-07 | 浙江大学 | Fuel cell using conductive polymer modified carbon based cobaltous hydroxide composite catalyst |
| CN101549304A (en) * | 2009-05-07 | 2009-10-07 | 浙江大学 | Method for preparing conductive polymer modified carbon based cobaltous hydroxide composite catalyst |
Non-Patent Citations (2)
| Title |
|---|
| S.R.Sivakkumar.Performance evaluation of CNT/Polypyrrole/MnO2 Composite Electrodes for Electrochemical Capacitors.《Electrochimica Acta》.2007,第52卷(第25期),第7378页右栏第3段. |
| S.R.Sivakkumar.Performance evaluation of CNT/Polypyrrole/MnO2 Composite Electrodes for Electrochemical Capacitors.《Electrochimica Acta》.2007,第52卷(第25期),第7378页右栏第3段. * |
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