CN102856563A - Non-metal oxygen reduction electrode and preparation method thereof - Google Patents
Non-metal oxygen reduction electrode and preparation method thereof Download PDFInfo
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- CN102856563A CN102856563A CN2012103535822A CN201210353582A CN102856563A CN 102856563 A CN102856563 A CN 102856563A CN 2012103535822 A CN2012103535822 A CN 2012103535822A CN 201210353582 A CN201210353582 A CN 201210353582A CN 102856563 A CN102856563 A CN 102856563A
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Abstract
The invention discloses a preparation method of a non-metal oxygen reduction electrode. The method includes: dispersing an oxidant and alkali inhibitor-containing solution on a conducting medium surface, volatilizing the solvent, exposing the conducting medium with a mixture layer of the oxidant and the alkali inhibitor to an ethylenedioxythiophene monomer containing atmosphere, making the ethylenedioxythiophene monomer polymerized on the conducting medium surface at 7DEG C-120DEG C to form a polymer catalyst. The invention also discloses a non-metal oxygen reduction electrode. The catalyst obtained by the invention is a high polymer material poly(3, 4-ethylenedioxythiophene), which has oxygen reduction catalytic activity, does not have the problems of displacement, aggregation, poisoning and the like of traditional metal catalysts, and has a low cost. The oxygen reduction electrode provided in the invention has good catalytic effects both in alkaline and acidic environments, and can be applied in proton exchange membrane fuel cells, direct alcohol fuel cells, alkaline fuel cells, metal-air cells and other fields.
Description
Technical field
The application belongs to field of batteries, particularly relates to a kind of nonmetal oxygen reduction electrode and preparation method thereof.
Background technology
No matter be to use the fuel cell of needs or the metal-air cell that energy storage needs as the energy, all need to have the oxygen reduction electrode of greater efficiency.Traditional oxygen reduction electrode catalyst is metal platinum, and it has higher current efficiency, but also exists a lot of problems to limit its use and life-span.For example, platinum is as a kind of scarce resource, and is expensive, improved the cost of battery.Secondly, platinum is unfixing in use, so be easy to occur assembling and the displacement phenomenon, greatly reduces its service efficiency.Especially, in the battery of alcohol fuel battery or air supply, all be difficult to avoid the existence of carbon monoxide, and platinum is very responsive to carbon monoxide, easily loses catalytic activity, causes battery efficiency sharply to descend.In order to overcome these problems, people have researched and developed the metal electrode of many non-platinum classes and base metal class, but still in various degree the existence, particularly carbon monoxide of these problems causes the problem of catalysqt deactivation to be difficult to overcome.
Summary of the invention
In view of this, purpose of the present invention provides a kind of nonmetal oxygen reduction electrode and preparation method thereof, the problems such as displacement, gathering and poisoning of traditional metal catalyst can not occur in the nonmetal oxygen reduction electrode that obtains, and are with low cost, and in alkalescence, sour environment preferably catalytic effect arranged.
For achieving the above object, the invention provides following technical scheme:
The present invention discloses a kind of preparation method of nonmetal oxygen reduction electrode, wherein, the method is: be dispersed with the solution that contains oxidant and alkali inhibitor on the conducting medium surface, to be exposed in the atmosphere that contains the ethylenedioxy thiophene monomer with the conducting medium of the mixture layer of oxidant and alkali inhibitor behind the solvent flashing, make the ethylenedioxy thiophene monomer under 7 ℃ ~ 120 ℃ temperature, form polyalcohol catalyst in the conducting medium surface aggregate.
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, also comprise the process that the conducting medium that will be loaded with polyalcohol catalyst washs, this washing methods is with the aqueous solvent washing by soaking, and then solvent flashing obtains nonmetal oxygen reduction electrode.
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, described oxidant comprises trivalent iron salt, and described alkali inhibitor comprises little molecule alkali, the mol ratio of described alkali inhibitor and oxidant is 0 ~ 2, and the content of oxidant is 0wt% ~ 40wt% in the described solution.
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, the content of oxidant is 20wt% ~ 40wt% in the described solution.
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, described oxidant is p-methyl benzenesulfonic acid iron or iron chloride.
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, described little molecule alkali is pyridine, pyrroles, imidazoles or four replacement (dimethylamino) ethene.
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, described conducting medium resistivity is less than 1 Ω cm
2
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, the solvent in the described solution comprises small molecular alcohol.
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, described small molecular alcohol is methyl alcohol, ethanol, isopropyl alcohol or butanols.
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, the described solution that contains oxidant and alkali inhibitor is to be sprayed on the conducting medium surface, and this spraying method is for using spray gun to spray at conducting medium under nitrogen pressure.
Preferably, in the preparation method of above-mentioned nonmetal oxygen reduction electrode, the described atmosphere that contains the ethylenedioxy thiophene monomer refers to the mobile lower volatility ethylenedioxy thiophene monomer of bringing into of air, nitrogen or argon gas.
The invention also discloses a kind of nonmetal oxygen reduction electrode that is obtained by above-mentioned preparation method.
The invention also discloses a kind of nonmetal oxygen reduction electrode, comprise conducting medium and catalyst, wherein, described catalyst is by poly-3,4-ethylenedioxy thiophene and little molecular dopant consist of, the repetitive of poly-3,4-ethylene dioxythiophene and the mol ratio of little molecular dopant are 1 ~ 10, and described little molecular dopant is little molecule acid and/or little molecule alkali.
Preferably, in above-mentioned nonmetal oxygen reduction electrode, described little molecule acid is selected from one or more in p-methyl benzenesulfonic acid, the p-methyl benzenesulfonic acid that is partly replaced, hydrochloric acid, hydrogen bromide, hydrogen iodide, myristyl sulfonic acid, 4-vinyl benzenesulfonic acid and the camphorsulfonic acid.
Preferably, in above-mentioned nonmetal oxygen reduction electrode, described little molecule alkali is selected from one or more in pyridine, pyrroles, imidazoles and four replacement (dimethylamino) ethene.
Preferably, in above-mentioned nonmetal oxygen reduction electrode, described conducting medium resistivity is less than 1 Ω cm
2
Compared with prior art, the invention has the advantages that: electrode catalyst of the present invention is a kind of macromolecular material, has the hydrogen reduction catalytic activity, and the problems such as displacement, gathering and poisoning of traditional metal catalyst can not occur, and with low cost.Oxygen reduction electrode of the present invention has preferably catalytic effect in alkalescence, sour environment, can be applicable to Proton Exchange Membrane Fuel Cells, direct alcohol fuel cell, the fields such as alkaline fuel cell and metal-air battery.
Description of drawings
In order to be illustrated more clearly in the embodiment of the present application or technical scheme of the prior art, the below will do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art, apparently, the accompanying drawing that the following describes only is some embodiment that put down in writing among the application, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Figure 1 shows that the structural representation of nonmetal oxygen reduction electrode in the specific embodiment of the invention;
Figure 2 shows that the nonmetal oxygen reduction electrode that obtains in the specific embodiment of the invention quiet cycle volt-ampere curve in the saturated 0.1M potassium hydroxide aqueous solution of oxygen, its sweep speed is 0.1V/s;
Figure 3 shows that the polyalcohol catalyst that obtains in the specific embodiment of the invention quiet cycle volt-ampere curve in the saturated 0.1M potassium hydroxide aqueous solution of oxygen, its sweep speed is 0.01V/s;
Figure 4 shows that the polarization curve the when polyalcohol catalyst that obtains in the specific embodiment of the invention rotating speed in the saturated 0.1M potassium hydroxide aqueous solution of oxygen is 3000rpm, its sweep speed is 0.01V/s;
Figure 5 shows that the polarization curve the when polyalcohol catalyst that obtains in the specific embodiment of the invention rotating speed in the saturated 0.05M aqueous sulfuric acid of oxygen is 3000rpm, its sweep speed is 0.01V/s.
Embodiment
Conducting polymer has special structure and electrical properties, and wherein poly-3,4-ethylene dioxythiophene (PEDOT) is one of best conducting polymer of conductivity, and this material has high oxygen permeability and excellent environmental stability simultaneously.The people such as Barsukov studied the hydrogen reduction process of the PEDOT that obtains by chemical oxidising polymerisation, thought that PEDOT does not have catalytic activity [Electrochimica Acta, v50, p1675].At present, PEDOT is often used as the carrier of catalyst in the oxygen reduction electrode because of its loose structure and good conduction property.
As previously mentioned, traditional oxygen reduction electrode catalyst is that its cost is high take the metallic catalyst of platinum as the basis, anthracemia and deficiency such as displacement phenomenon etc. are difficult to overcome, for this reason, this case inventor has proposed technical scheme of the present invention through studying for a long period of time and putting into practice.
Further say, nonmetal oxygen reduction electrode catalyst of the present invention is the poly-3,4-ethylene dioxythiophene of a kind of macromolecular material, and material is nonmetal and concrete hydrogen reduction catalytic activity own, the problems such as displacement, gathering and poisoning of traditional metal catalyst can not occur, and with low cost.Oxygen reduction electrode of the present invention has preferably catalytic effect in alkalescence, sour environment, can be applicable to Proton Exchange Membrane Fuel Cells, direct alcohol fuel cell, the fields such as alkaline fuel cell and metal-air battery.
This nonmetal oxygen reduction electrode adopts gas-phase synthesizing method to make, its method is: be dispersed with the solution that contains oxidant and alkali inhibitor on the conducting medium surface, to be exposed in the atmosphere that contains the ethylenedioxy thiophene monomer with the conducting medium of the mixture layer of oxidant and alkali inhibitor behind the solvent flashing, make the ethylenedioxy thiophene monomer under 7 ℃ ~ 120 ℃ temperature, form polyalcohol catalyst in the conducting medium surface aggregate.
In the said method, oxidant preferably adopts trivalent iron salt (such as p-methyl benzenesulfonic acid iron, iron chloride etc., but be not limited to this), the alkali inhibitor is preferably the little molecule alkali such as pyridine, solvent be preferably alcohols solvent (such as methyl alcohol, ethanol, isopropyl alcohol, butanols etc., but be not limited to this).Wherein the mol ratio of alkali inhibitor and molysite is between 0 ~ 2, is preferably between 0.75 ~ 1; Iron salt solutions concentration is 0% ~ 40%(mass fraction), be preferably 5% ~ 40%, more elect as greater than 20%, and be less than or equal to 40%.
In the said method, the atmosphere that contains the ethylenedioxy thiophene monomer refers to air, nitrogen or the argon gas lower volatility ethylenedioxy thiophene monomer of bringing into that flows, and polymerization temperature is preferably 7 ~ 120 ℃, especially is preferably 50 ℃.Preferably ambient humidity is controlled at 15% ~ 60% in the polymerization process.
In the said method, also comprise the process that the conducting medium that will be loaded with polyalcohol catalyst washs, this washing methods is that then solvent flashing obtains nonmetal oxygen reduction electrode with aqueous solvent (such as small molecule alcohol, water, oxolane, dimethyl formamide or methyl-sulfoxide etc.) washing by soaking.The purpose of washing is to remove remaining oxidant, alkali inhibitor and byproduct of reaction.
In the said method, conducting medium resistivity is preferably less than 1 Ω cm
2, conducting medium is preferably the porous carbon paper.
Join shown in Figure 1, the embodiment of the invention also discloses a kind of nonmetal oxygen reduction electrode, comprise conducting medium 1 and catalyst 2, described catalyst 2 is by poly-3,4-ethylenedioxy thiophene and little molecular dopant consist of, the repetitive of poly-3,4-ethylene dioxythiophene and the mol ratio of little molecular dopant are 1 ~ 10, and described little molecular dopant is little molecule acid and/or little molecule alkali.
The nonmetal hydrogen reduction catalysis electrode that the embodiment of the invention obtains is a kind of macromolecular material, and the problems such as displacement, gathering and poisoning of traditional metal catalyst can not occur, and with low cost.Oxygen reduction electrode in the embodiment of the invention has preferably catalytic effect in alkalescence, sour environment, can be applicable to Proton Exchange Membrane Fuel Cells, direct alcohol fuel cell, the fields such as alkaline fuel cell and metal-air battery.
The present invention is described further by the following example: according to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described concrete material ratio of embodiment, process conditions and result thereof only are used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
The synthetic method of the nonmetal oxygen reduction electrode that the present embodiment is related comprises the steps:
(1) the p-methyl benzenesulfonic acid dissolved ferric iron being obtained mass fraction in n-butanol is 40% solution, then adds the pyridine with p-methyl benzenesulfonic acid iron equimolar amounts, mixes.
(2) under humidity is 50% environment, and the solution that step (1) obtains is sprayed at porous carbon paper surface with spray gun under stream of nitrogen gas, the temperature of porous carbon paper is 70 ℃;
(3) the porous carbon paper that step (2) is obtained shifts in polymerization reaction chamber, polymerization film formation in the EDOT monomer of volatilization, and humidity 20%, nitrogen flow rate 150 mL/min, temperature is controlled at 50
oC, two hours time;
(4) the porous carbon paper washing by soaking in ethanol that is loaded with polyalcohol catalyst that step (3) is obtained is removed remaining oxidant, alkali inhibitor and byproduct of reaction, namely obtains nonmetal oxygen reduction electrode.
Porous carbon paper used in the present embodiment derives from Shanghai Hesen Electric Co., Ltd, model HCP010, thickness 0.1 ± 0.01mm, density 0.78g/cm
3, the porosity 75%, resistivity 2.5m Ω.
In three-electrode system, take the metal platinum electrode as to electrode, saturated calomel is reference electrode, above-mentioned nonmetal oxygen reduction electrode is work electrode, the 0.1M potassium hydroxide aqueous solution that oxygen is saturated is electrolyte, carry out cyclic voltammetry scan at 0.2V CHI electrochemical workstation with Shanghai occasion China in the-1.0V voltage range, sweep speed is 0.1V/s, and the gained cyclic voltammetry curve as shown in Figure 2.A hydrogen reduction characteristic peak is clearly arranged among the figure, and spike potential is-0.529V(vs.Hg
2SO
4/ Hg), peak current is 10.76mA/cm
2Illustrate that this electrode has preferably catalytic activity for hydrogen reduction.This electrode can be applied to Proton Exchange Membrane Fuel Cells, direct alcohol fuel cell, alkaline fuel cell and metal-air battery.
In order to further specify the catalytic activity of the polyalcohol catalyst that obtains, we use the same method this polyalcohol catalyst and are deposited on the glass carbocyclic ring disc electrode, scan with Autolab electrochemical workstation more accurately.In this three-electrode system, take glass-carbon electrode as to electrode, be reference electrode Ag/AgCl(3M), the ring-disc electrode that is loaded with polyalcohol catalyst is work electrode.Fig. 3 is the cyclic voltammetry curve under its static state, sweep speed is 0.01V/s, electrolyte is the saturated 0.1M potassium hydroxide aqueous solution of oxygen. a hydrogen reduction characteristic peak is clearly arranged among the figure, and spike potential is-0.376V(vs. Ag/AgCl), peak current is 0.21mA/cm
2Illustrate that this electrode has preferably catalytic activity for hydrogen reduction.Fig. 4 is the polarization curve of this disc electrode when rotary speed is 3000rpm, sweep speed 0.01V/s, and the hydrogen reduction peak current reaches 2.48 mA/cm
2
In order to further specify the catalytic activity of polyalcohol catalyst in acid environment that obtains, the sulfuric acid solution that we select the saturated 0.05M of oxygen is electrolyte, take glass-carbon electrode as to electrode, Ag/AgCl(3M) be reference electrode, the ring-disc electrode that is loaded with polyalcohol catalyst is work electrode, the rotary speed of disc electrode is 3000rpm, and sweep speed is 0.01V/s, and its current/voltage polarization curve as shown in Figure 5.As can be seen from the figure, this polyalcohol catalyst still demonstrates certain catalytic activity under acid environment, and the hydrogen reduction current potential is-0.06V(vs. Ag/AgCl), the hydrogen reduction electric current reaches 0.032mA/cm
2
In sum, nonmetal oxygen reduction electrode catalyst of the present invention is the poly-3,4-ethylene dioxythiophene of a kind of macromolecular material, and material is nonmetal and concrete hydrogen reduction catalytic activity own, the problems such as displacement, gathering and poisoning of traditional metal catalyst can not occur, and with low cost.Oxygen reduction electrode of the present invention has preferably catalytic effect in alkalescence, sour environment, can be applicable to Proton Exchange Membrane Fuel Cells, direct alcohol fuel cell, the fields such as alkaline fuel cell and metal-air battery.
Need to prove, in this article, relational terms such as the first and second grades only is used for an entity or operation are separated with another entity or operating space, and not necessarily requires or hint and have the relation of any this reality or sequentially between these entities or the operation.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thereby not only comprise those key elements so that comprise process, method, article or the equipment of a series of key elements, but also comprise other key elements of clearly not listing, or also be included as the intrinsic key element of this process, method, article or equipment.In the situation that not more restrictions, the key element that is limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment that comprises described key element and also have other identical element.
The above only is the application's embodiment; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the application's principle; can also make some improvements and modifications, these improvements and modifications also should be considered as the application's protection range.
Claims (16)
1. the preparation method of a nonmetal oxygen reduction electrode, it is characterized in that, the method is: be dispersed with the solution that contains oxidant and alkali inhibitor on the conducting medium surface, to be exposed in the atmosphere that contains the ethylenedioxy thiophene monomer with the conducting medium of the mixture layer of oxidant and alkali inhibitor behind the solvent flashing, make the ethylenedioxy thiophene monomer under 7 ℃ ~ 120 ℃ temperature, form polyalcohol catalyst in the conducting medium surface aggregate.
2. the preparation method of nonmetal oxygen reduction electrode according to claim 1, it is characterized in that: also comprise the process that the conducting medium that will be loaded with polyalcohol catalyst washs, this washing methods is with the aqueous solvent washing by soaking, and then solvent flashing obtains nonmetal oxygen reduction electrode.
3. the preparation method of nonmetal oxygen reduction electrode according to claim 1, it is characterized in that: described oxidant comprises trivalent iron salt, described alkali inhibitor comprises little molecule alkali, and the mol ratio of described alkali inhibitor and oxidant is 0 ~ 2, and the content of oxidant is 0wt% ~ 40wt% in the described solution.
4. the preparation method of nonmetal oxygen reduction electrode according to claim 3, it is characterized in that: the content of oxidant is 20wt% ~ 40wt% in the described solution.
5. the preparation method of nonmetal oxygen reduction electrode according to claim 3, it is characterized in that: described oxidant is p-methyl benzenesulfonic acid iron or iron chloride.
6. the preparation method of nonmetal oxygen reduction electrode according to claim 3 is characterized in that: described little molecule alkali is that pyridine, pyrroles, imidazoles or four replace (dimethylamino) ethene.
7. the preparation method of nonmetal oxygen reduction electrode according to claim 1, it is characterized in that: described conducting medium resistivity is less than 1 Ω cm
2
8. the preparation method of nonmetal oxygen reduction electrode according to claim 1, it is characterized in that: the solvent in the described solution comprises small molecular alcohol.
9. the preparation method of nonmetal oxygen reduction electrode according to claim 8, it is characterized in that: described small molecular alcohol is methyl alcohol, ethanol, isopropyl alcohol or butanols.
10. the preparation method of nonmetal oxygen reduction electrode according to claim 1, it is characterized in that: the described solution that contains oxidant and alkali inhibitor is to be sprayed on the conducting medium surface, and this spraying method is for using spray gun to spray at conducting medium under nitrogen pressure.
11. the preparation method of nonmetal oxygen reduction electrode according to claim 1 is characterized in that: the described atmosphere that contains the ethylenedioxy thiophene monomer refers to the mobile lower volatility ethylenedioxy thiophene monomer of bringing into of air, nitrogen or argon gas.
12. the described nonmetal oxygen reduction electrode of claim 1 to 11 any one.
13. nonmetal oxygen reduction electrode, comprise conducting medium and catalyst, it is characterized in that: described catalyst is by poly-3,4-ethylenedioxy thiophene and little molecular dopant consist of, poly-3, the repetitive of 4-ethylenedioxy thiophene and the mol ratio of little molecular dopant are 1 ~ 10, and described little molecular dopant is little molecule acid and/or little molecule alkali.
14. nonmetal oxygen reduction electrode according to claim 13 is characterized in that: described little molecule acid is selected from one or more in p-methyl benzenesulfonic acid, the p-methyl benzenesulfonic acid that is partly replaced, hydrochloric acid, hydrogen bromide, hydrogen iodide, myristyl sulfonic acid, 4-vinyl benzenesulfonic acid and the camphorsulfonic acid.
15. nonmetal oxygen reduction electrode according to claim 13 is characterized in that: described little molecule alkali is selected from one or more in pyridine, pyrroles, imidazoles and four replacement (dimethylamino) ethene.
16. nonmetal oxygen reduction electrode according to claim 13 is characterized in that: described conducting medium resistivity is less than 1 Ω cm
2
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103113558A (en) * | 2013-01-31 | 2013-05-22 | 深圳新宙邦科技股份有限公司 | Conductive high polymer, oxidizer for synthesis thereof and solid capacitor |
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| CN101815740A (en) * | 2007-07-09 | 2010-08-25 | 帝国创新有限公司 | Highly conductive and stable transparent conducting polymer films |
| CN102604334A (en) * | 2012-02-07 | 2012-07-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Self-supporting transparent highly-conductive poly-3,4-ethylenedioxythiophene (PEDOT) film and preparation method of the film |
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| CN101815740A (en) * | 2007-07-09 | 2010-08-25 | 帝国创新有限公司 | Highly conductive and stable transparent conducting polymer films |
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| CN103113558A (en) * | 2013-01-31 | 2013-05-22 | 深圳新宙邦科技股份有限公司 | Conductive high polymer, oxidizer for synthesis thereof and solid capacitor |
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