CN101800325A - Alkaline direct dimethyl ether fuel cell - Google Patents
Alkaline direct dimethyl ether fuel cell Download PDFInfo
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- CN101800325A CN101800325A CN201010132183A CN201010132183A CN101800325A CN 101800325 A CN101800325 A CN 101800325A CN 201010132183 A CN201010132183 A CN 201010132183A CN 201010132183 A CN201010132183 A CN 201010132183A CN 101800325 A CN101800325 A CN 101800325A
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- dimethyl ether
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- carbon
- fuel cell
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000000446 fuel Substances 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 claims abstract description 121
- 239000000243 solution Substances 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000005341 cation exchange Methods 0.000 claims abstract description 9
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 109
- 229910052799 carbon Inorganic materials 0.000 claims description 109
- 238000003756 stirring Methods 0.000 claims description 90
- 229920000128 polypyrrole Polymers 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 229910002848 Pt–Ru Inorganic materials 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 239000006229 carbon black Substances 0.000 claims description 37
- 150000003233 pyrroles Chemical class 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 19
- 239000004744 fabric Substances 0.000 claims description 19
- 239000006260 foam Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 239000012279 sodium borohydride Substances 0.000 claims description 18
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 5
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 238000010248 power generation Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000638 solvent extraction Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000010931 gold Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 4
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to an alkaline fuel cell, which aims to provide an alkaline direct dimethyl ether fuel cell. A cation exchange membrane or an anion exchange membrane is used as a membrane of the fuel cell for partitioning an anode and a cathode, an alkaline dimethyl ether solution contained in an anode catalyst carrier is used as an electrolyte, and the alkaline dimethyl ether solution is an aqueous solution in which dimethyl ether is saturated and the concentration of NaOH or KOH is 1-6 mol/L. In the invention, the dimethyl ether dissolved in lye is used as fuel, which can greatly improve the power generation performance of the direct dimethyl ether fuel cell. The alkaline direct dimethyl ether fuel cell can be applied to portable and mobile power supplies in large-scale commercial applications. An anode catalyst is beneficial to exerting the performance of a cocatalyst on improving the Co poisoning resisting performance of Pt, thereby improving the activity of the catalyst and improving the power generation performance of the dimethyl ether fuel cell. Likewise, the activity of a cathode catalyst can be improved, and the oxygen reduction reaction kinetics can be improved, thereby improving the power generation performance of the dimethyl ether fuel cell.
Description
Technical field
The present invention relates to a kind of alkaline fuel cell of working at low temperatures, more particularly, the present invention relates to a kind of is fuel with the alkaline solution that is dissolved with dimethyl ether directly, and amberplex is electrolytical fuel cell.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is considered to portable and compact power field one of the most promising technology.Though the PEMFC technology reaches its maturity, yet its commercialization also faces an insoluble problem, the i.e. production of hydrogen and accumulating.The accumulating of hydrogen mainly contains dual mode: the first, and gas cylinder storage hydrogen, shortcoming is that volumetric specific energy is low, to the equipment requirements height, and has certain potential safety hazard; The second, utilize reformation gas to give the fuel cell charging, this must make fuel cell system complicated, increases cost.
People attempt seeking other alternative fuel to overcome the technology barrier of PEMFC, and are wherein in the majority with organic molecule.For direct methanol fuel cell, there is not the problem of accumulating difficulty in fuel, but reactivity is low and very easily make the infiltration between negative electrode and anode of catalyst poisoning, especially methyl alcohol can cause the heavy losses of battery performance.To studies show that of direct alcohol fuel cell, there is the C-C key in the molecular structure of ethanol, thereby its thorough electrochemical oxidation is generated CO
2Very difficulty can generate various accessory substances in this process, in addition usually such as aldehyde and ester; For avoiding molecular structure to have the C-C key, someone attempts using dimethoxymethane (DMM) and trimethoxy-methane (TMM) to act as a fuel, but have methyl alcohol to generate behind two kinds of oxidation operations, still do not solve the problem that fuel infiltration causes battery performance to reduce, preparation cost is also than higher; Formic acid and formaldehyde are lower as the energy density of battery fuel, and formic acid has corrosivity, the formaldehyde unstable chemcial property, and the both is toxic in addition.So all there is the problem on technology, economy or the safety in the direct fuel cell that these organic molecules act as a fuel.
From the molecular structure angle, there is not the C-C key in the dimethyl ether molecule, easily by complete oxidation.The molecular structure symmetry, dipole moment is less, can effectively reduce dimethyl ether and H
3 +Combination between the O reduces the fuel infiltration that the electricity towing causes.On the physical property, dimethyl ether and propane are similar, so the infrastructure in the propane transportation can directly be that dimethyl ether is used.People have proposed the direct dimethyl ether fuel battery (DDFC) that acts as a fuel with dimethyl ether (DME).DDFC is a kind of electrochemical reaction appts that the chemical energy that directly will be stored in fuel dimethyl ether and oxygen is converted into electric energy.Propose a kind of intermediate temperature solid oxide fuel cell as Chinese invention patent application CN1560951 and utilize the dimethyl ether direct generation of electricity.Chinese invention patent application CN101013755 proposes a kind of normal temperature work dimethyl ether fuel battery, its dimethyl ether feeding device comprises the dimethyl ether steel cylinder and fills the pressurized tank of water, set up dimethyl ether recycle and reuse system, comprise knockout drum, purification pot, cooling tank and constant flow pump, wherein the dimethyl ether steel cylinder is through control valve control cut-in pressure jar, and the pipeline of pressurized tank through being provided with constant flow pump, flowmeter and control valve connected the anode inlet of fuel cell.
When electrolyte is cation-exchange membrane, supply with gas of dimethyl ether molecule dehydrogenation generation electrochemical oxidation reactions under the catalytic action of catalyst of anode, discharge electronics and generate CO
2And the hydrogen ion (H that anode produces
+) move to negative electrode by dielectric film.Because electrolyte can only can not pass through electronics by ion, the electronics that discharges externally moves the formation electric current in the circuit.Work as H
+After arriving negative electrode, on cathod catalyst with O
2And the electronics that moves from external circuit is in conjunction with generating H
2O.Its electrode and cell reaction process are as follows, and wherein, negative electrode and anode potential are the electrode potentials with respect to standard hydrogen electrode (SHE):
Anode: CH
3OCH
3+ 3H
2O → 2CO
2+ 12H
++ 12e
-E
o=0.036V vs.SHE
Negative electrode: 3O
2+ 12H
++ 12e
-→ 6H
2O E
o=1.23V vs.SHE
Battery: CH
3OCH
3+ 3O
2→ 3H
2O+2CO
2E
o=1.194V vs.SHE
Yet not only dimethyl ether reactivity under acid condition is relatively poor, and the electrochemical reduction activity of oxygen is also very poor.Therefore dimethyl ether is dissolved in the water, as the fuel of Proton Exchange Membrane Fuel Cells, the performance of its performance Proton Exchange Membrane Fuel Cells when being fuel with hydrogen or methanol aqueous solution.
Summary of the invention
The technical problem to be solved in the present invention is that improvement is the performance of the direct dimethyl ether fuel battery of fuel with the dimethyl ether, and a kind of alkaline fuel cell of working at low temperatures is provided.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of alkaline direct dimethyl ether fuel cell is provided, cut off anode and negative electrode with cation-exchange membrane or anion-exchange membrane as barrier film, the alkaline dimethyl ether solution that contains with anode catalyst carrier is electrolyte, and described alkaline dimethyl ether solution is that dimethyl ether is saturated, NaOH or KOH concentration are the aqueous solution of 1～6 mol.
Among the present invention, described fuel cell has the following structure of arranging successively at horizontal direction: plate, anode catalyst carrier, anode catalyst, barrier film, cathod catalyst, cathode catalysis agent carrier and cathode plate; Sealing is all realized with sealing ring in the two ends up and down of fuel cell, and its negative terminal is drawn by anode catalyst carrier, and positive terminal is drawn by cathode plate; Establish the gas of dimethyl ether inlet in the anode catalyst carrier bottom, the tail gas outlet is established on its top; Described cathode catalysis agent carrier is carbon paper or the carbon cloth of handling through hydrophobic, and described cathode plate has air flue; Described anode catalyst carrier is carbon paper, carbon cloth or the nickel foam through hydrophilic treated, and filling contains the NaOH of dimethyl ether or the KOH aqueous solution as electrolyte.
Among the present invention, as cathod catalyst, its negative electrode makes by following manner described fuel cell with the polypyrrole modifying carbon supported noble metal catalyst:
(1) preparation polypyrrole modifying carbon supported noble metal:
Carbon black is distributed in water, methyl alcohol or the chloroform is made into suspension-turbid liquid, its mass ratio is 1: 15; Adding glacial acetic acid or salt acid for adjusting pH value is 2.5～3, stirring at room 10～30min; Mass ratio by carbon black and pyrroles is that 1: 0.05～0.3 adding pyrroles stirs 5～10min, adds the chloride of gram Pt, Pd or Au then; The H that adds 0.05～0.1 gram mass behind stirring at room 3～10h again
2O
2Behind stirring at room 3～10h, be heated to 70～90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 30～60min, natural cooling; After filtering with deionized water wash, behind 70～90 ℃ of drying 6～12h of vacuum at Ar or N
2Inert atmosphere under 300～600 ℃ the insulation 1～5h heat-treat, make corresponding polypyrrole modifying carbon supported noble metal catalyst;
(2) with the polytetrafluoroethylene suspension-turbid liquid of polypyrrole modifying carbon supported noble metal catalyst, water, 5wt.%, absolute ethyl alcohol according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation form slurry, be coated on carbon paper or carbon cloth that hydrophobic is handled, naturally dry and get final product, the mass ratio of polypyrrole modifying carbon supported noble metal catalyst and carbon paper or carbon cloth is 1: 10～100.
Among the present invention, this fuel cell carries the Pt-Ru catalyst as anode catalyst with polypyrrole modifying carbon, and the mass ratio of Pt-Ru catalyst and polypyrrole modifying carbon carrier is 1: 1～9; The mass ratio of Pt and Ru is 1: 0.5～1 in the catalyst; Described anode catalyst makes by following manner:
Carbon black is distributed in water, methyl alcohol or the chloroform is made into suspension-turbid liquid, its mass ratio is 1: 15; Adding glacial acetic acid or salt acid for adjusting pH value is 2.5～3, stirring at room 10～30min; Mass ratio by carbon black and pyrroles is that 1: 0.05～0.3 adding pyrroles stirs 5～10min, and the mass ratio that adds Pt and Ru then is 1: 0.5～1 PtCl
2And RuCl
2The H that adds 0.05～0.1 gram mass behind stirring at room 3～10h again
2O
2Behind stirring at room 3～10h, be heated to 70～90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 30～60min, natural cooling; After filtering with deionized water wash, behind 70～90 ℃ of drying 6～12h of vacuum at Ar or N
2Inert atmosphere under 300～600 ℃ the insulation 1～5h heat-treat, make polypyrrole modifying carbon and carry the Pt-Ru catalyst.
Among the present invention, the anode of this fuel cell makes by following manner: carry the Pt-Ru catalyst by described polypyrrole modifying carbon: the poly-vinyl alcohol solution of water: 5wt.% or perfluor sulfoacid resin solution: the mass ratio of absolute ethyl alcohol is 1: 3: 2～7: 3～6 hybrid modulation slurries, be coated to then on carbon paper, carbon cloth or the nickel foam through hydrophilic treated, naturally dry and get final product, the mass ratio that polypyrrole modifying carbon carries Pt-Ru catalyst and carbon paper, carbon cloth or nickel foam is 1: 10～100.
Among the present invention, when directly dimethyl ether fuel battery discharged, DME generation electrochemical oxidation generated water and carbon dioxide on anode, and the electrochemical reduction that oxygen takes place on negative electrode is simultaneously consumed water formation hydroxide ion, and its electrode reaction and cell reaction are as follows:
Anode: CH
3OCH
3+ 12OH
-→ 2CO
2+ 9H
2O+12e
-E
o=-0.797V vs.SHE
Negative electrode: 3O
2+ 6H
2O+12e
-→ 12OH
-E
o=0.401V vs.SHE
Battery: CH
3OCH
3+ 3O
2→ 3H
2O+2CO
2E
o=1.194V vs.SHE
Tested DME in acid medium, neutral medium and alkaline medium the electrochemistry oxygen galvanic current and the relation of current potential, as shown in Figures 1 to 3.The result shows that in alkaline solution, the reactivity of being not only dimethyl ether improves along with the increase of concentration of lye, and as shown in Figure 4, the electrochemical reduction activity of oxygen also can improve when DME was dissolved in alkaline solution and acts as a fuel the fuel of battery, as shown in Figure 6.Thereby make direct dimethyl ether fuel battery performance be improved, as shown in Figure 7.
Compared with prior art, the invention has the beneficial effects as follows:
Than the dimethyl ether of the aqueous solution that is dissolved in water, acid or salt, the dimethyl ether that is dissolved in the alkaline solution has bigger reactivity, alleviates the catalyst poisoning that intermediate product CO that dimethyl ether produces in electrochemical oxidation process is caused greatly.Use the dimethyl ether that is dissolved in the alkali lye to be fuel, can improve the power generation performance of direct dimethyl ether fuel battery greatly.The dimethyl ether wide material sources, in conjunction with the advantage of coal resources in China, dimethyl ether large-scale production cost is lower than most of fuel, is its sharpest edges that are applied to fuel cell.The DDFC technology that the dimethyl ether energy is combined with the PEMFC technology and form can be applicable to the portable and portable power supply of large-scale commercial applications application, as electric automobile, and electronic product and military equipment etc.
Adopt polypyrrole modifying carbon to carry the Pt-Ru catalyst as anode catalyst, polypyrrole on carbon black can make the distribution disperse more of Pt-Ru particle, evenly, particle size is more tiny, help to bring into play the Ru co-catalyst to improving the anti-CO poisoning performance of Pt, improve activity of such catalysts thus, improve the power generation performance of dimethyl ether fuel battery.Equally, for cathod catalyst, polypyrrole can make the distribution disperse more of Pt, Pd, Au particle, evenly, and particle size is more tiny, improves activity of such catalysts thus, improves oxygen reduction reaction dynamics, thereby improves the power generation performance of dimethyl ether fuel battery.
Figure of description
Fig. 1 be among the embodiment 1 dimethyl ether at 0.5M L
-1H
2SO
4In the electrochemistry oxygen galvanic current and the relation of current potential, it is catalyst that polypyrrole modifying carbon carries the Pt-Ru catalyst.
Fig. 2 be among the embodiment 1 dimethyl ether at 0.5M L
-1Na
2SO
4In the electrochemistry oxygen galvanic current and the relation of current potential, it is catalyst that polypyrrole modifying carbon carries the Pt-Ru catalyst.
Fig. 3 be among the embodiment 1 dimethyl ether at 1M L
-1NaOH in the electrochemistry oxygen galvanic current and the relation of current potential, it is catalyst that polypyrrole modifying carbon carries the Pt-Ru catalyst.
Fig. 4 is the dimethyl ether electrochemistry oxygen galvanic current in variable concentrations NaOH solution among the embodiment.
The structure of the direct dimethyl ether fuel battery that Fig. 5 the present invention adopts.
Fig. 6 is an electrode polarization performance of using the direct dimethyl ether fuel battery of anion-exchange membrane among the embodiment 5.
Fig. 7 is the power generation performance that uses the direct dimethyl ether fuel battery of cation-exchange membrane among the embodiment 6.
Reference numeral among Fig. 5 is:
1 plate, 2 anode seal circles, 3 anode catalysts, 4 negative electrode sealing rings, 5 cathod catalysts, 6 cathode catalysis agent carriers, 7 air flues, 8 cathode plates, 9 negative electrode sealing rings, 10 barrier films, 11 anode seal circles, 12 negative terminals, 13 positive terminals, the outlet of 14 tail gas, 15 gas of dimethyl ether inlet, 16 nickel foam.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment 1-1: polypyrrole modifying carbon carries the Pt-Ru Preparation of Catalyst
Carbon black 10 gram is distributed to is made into suspension-turbid liquid in the water, its mass ratio is 1: 15; Adding glacial acetic acid adjusting pH value is 2.5, stirring at room 10min; Mass ratio by carbon black and pyrroles is that 1: 0.05 adding pyrroles stirs 5min, adds PtCl then
2And RuCl
2Each 0.6 gram; The H that adds 0.05 gram mass behind the stirring at room 3h again
2O
2After stopping up temperature stirring 3h, be heated to 70 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 30min, natural cooling; After filtering with deionized water wash, behind 70 ℃ of dry 6h of vacuum under the Ar inert atmosphere 300 ℃ of insulation 5h heat-treat, make polypyrrole modifying carbon and carry the Pt-Ru catalyst, the mass ratio of Pt-Ru catalyst and polypyrrole modifying carbon carrier is 1: 9; The mass ratio of Pt and Ru is 1: 1 in the catalyst.At 0.5M L
-1H
2SO
4, 0.5M L
-1Na
2SO
4With 1M L
-1The NaOH aqueous solution in, this catalyst is listed in Fig. 1,2,3 respectively to the electrochemical catalytic oxidation performance of DME.Through relatively finding that in alkaline solution polypyrrole modifying carbon carries the Pt-Ru catalyst and has good catalytic activity.Fig. 4 carries electrochemistry oxygen galvanic current on the Pt-Ru catalyst for the dimethyl ether in the variable concentrations NaOH solution at polypyrrole modifying carbon.
Embodiment 1-2: polypyrrole modifying carbon carries the Pt-Ru Preparation of Catalyst
Carbon black 10 gram is distributed to is made into suspension-turbid liquid in the methyl alcohol, its mass ratio is 1: 15; Adding the salt acid for adjusting pH value is 3, stirring at room 30min; Mass ratio by carbon black and pyrroles is that 1: 0.3 adding pyrroles stirs 10min, adds PtCl then
2And RuCl
2Each 0.6 gram; The H that adds 0.1 gram mass behind the stirring at room 10h again
2O
2Behind the stirring at room 10h, be heated to 90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 60min, natural cooling; After filtering with deionized water wash, behind 90 ℃ of dry 12h of vacuum at N
2The following 600 ℃ of insulation 1h of atmosphere heat-treat, and make polypyrrole modifying carbon and carry the Pt-Ru catalyst, and the mass ratio of Pt-Ru catalyst and polypyrrole modifying carbon carrier is 1: 9; The mass ratio of Pt and Ru is 1: 1 in the catalyst.
Embodiment 1-3: polypyrrole modifying carbon carries the Pt-Ru Preparation of Catalyst
Carbon black 10 gram is distributed to is made into suspension-turbid liquid in the methyl alcohol, its mass ratio is 1: 15; Adding the salt acid for adjusting pH value is 2.8, stirring at room 20min; Mass ratio by carbon black and pyrroles is that 1: 0.2 adding pyrroles stirs 20min, adds PtCl then
2And RuCl
2Each 0.6 gram; The H that adds 0.08 gram mass behind the stirring at room 6h again
2O
2Behind the stirring at room 6h, be heated to 80 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 50min, natural cooling; After filtering with deionized water wash, behind 80 ℃ of dry 9h of vacuum at N
2The following 500 ℃ of insulation 3h of atmosphere heat-treat, and make polypyrrole modifying carbon and carry the Pt-Ru catalyst, and the mass ratio of Pt-Ru catalyst and polypyrrole modifying carbon carrier is 1: 9; The mass ratio of Pt and Ru is 1: 1 in the catalyst.
Embodiment 2-1: anode preparation
Carbon black 1 gram is distributed to is made into suspension-turbid liquid in the methyl alcohol, its mass ratio is 1: 15; Adding the salt acid for adjusting pH value is 3, stirring at room 30min; Mass ratio by carbon black and pyrroles is that 1: 0.3 adding pyrroles stirs 10min, adds 0.8 gram PtCl then
2With 0.4 gram RuCl
2The H that adds 0.1 gram mass behind the stirring at room 10h again
2O
2Behind the stirring at room 10h, be heated to 90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 60min, natural cooling; After filtering with deionized water wash, behind 90 ℃ of dry 12h of vacuum under blanket of nitrogen 600 ℃ of insulation 5h heat-treat, make polypyrrole modifying carbon and carry the Pt-Ru catalyst, the mass ratio of Pt-Ru catalyst and polypyrrole modifying carbon carrier is 1: 1; The mass ratio of Pt and Ru is 1: 0.5 in the catalyst.
The polypyrrole modifying carbon that obtains is carried the poly-vinyl alcohol solution of Pt-Ru 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 of hydrophilic treated, naturally make anode after drying, the mass ratio that polypyrrole modifying carbon carries Pt-Ru catalyst and carbon paper is 1: 10.
Embodiment 2-2: anode preparation
Carbon black 1 gram is distributed to is made into suspension-turbid liquid in the methyl alcohol, its mass ratio is 1: 15; Adding the salt acid for adjusting pH value is 3, stirring at room 30min; Mass ratio by carbon black and pyrroles is that 1: 0.3 adding pyrroles stirs 10min, adds 0.6 gram PtCl then
2With 0.6 gram RuCl
2The H that adds 0.1 gram mass behind the stirring at room 10h again
2O
2After stopping up temperature stirring 10h, be heated to 90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 60min, natural cooling; After filtering with deionized water wash, behind 90 ℃ of dry 12h of vacuum under blanket of nitrogen 600 ℃ of insulation 5h heat-treat, make polypyrrole modifying carbon and carry the Pt-Ru catalyst, the mass ratio of Pt-Ru catalyst and polypyrrole modifying carbon carrier is 1: 1; The mass ratio of Pt and Ru is 1: 1 in the catalyst.
The polypyrrole modifying carbon that obtains is carried the poly-vinyl alcohol solution of Pt-Ru catalyst, water, 5wt.% and absolute ethyl alcohol according to 1: 3: 7: 6 mass ratio hybrid modulation form slurry, be coated on the nickel foam of hydrophilic treated, naturally make anode after drying, the mass ratio that polypyrrole modifying carbon carries Pt-Ru catalyst and nickel foam is 1: 100.
Embodiment 2-3: anode preparation
Carbon black 5 gram is distributed to is made into suspension-turbid liquid in the methyl alcohol, its mass ratio is 1: 15; Adding the salt acid for adjusting pH value is 3, stirring at room 30min; Mass ratio by carbon black and pyrroles is that 1: 0.3 adding pyrroles stirs 10min, adds 0.75 gram PtCl then
2With 0.45 gram RuCl
2The H that adds 0.1 gram mass behind the stirring at room 10h again
2O
2Behind the stirring at room 10h, be heated to 90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 60min, natural cooling; After filtering with deionized water wash, behind 90 ℃ of dry 12h of vacuum under blanket of nitrogen 600 ℃ of insulation 5h heat-treat, make polypyrrole modifying carbon and carry the Pt-Ru catalyst, the mass ratio of Pt-Ru catalyst and polypyrrole modifying carbon carrier is 1: 5; The mass ratio of Pt and Ru is 1: 0.75 in the catalyst.
The polypyrrole modifying carbon that obtains is carried the perfluor sulfoacid resin solution of Pt-Ru catalyst, water, 5wt.% and absolute ethyl alcohol according to 1: 3: 4: 4 mass ratio hybrid modulation form slurry, be coated on the carbon cloth of hydrophilic treated, naturally make anode after drying, the mass ratio that polypyrrole modifying carbon carries Pt-Ru catalyst and carbon cloth is 1: 20.
Embodiment 3-1: polypyrrole modifying carbon-containing palladium catalyst preparation
Carbon black 1 gram is distributed to is made into suspension-turbid liquid in the chloroform, its mass ratio is 1: 15; Adding glacial acetic acid adjusting pH value is 2.5, stirring at room 10min; Mass ratio by carbon black and pyrroles is that 1: 0.05 adding pyrroles stirs 5min, adds a gram PdCl then
2The H that adds 0.05 gram mass behind the stirring at room 3h again
2O
2Behind the stirring at room 3h, be heated to 70 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 30min, natural cooling; After filtering with deionized water wash, behind 70 ℃ of dry 12h of vacuum at N
2The following 300 ℃ of insulation 5h of atmosphere heat-treat, and make the polypyrrole modifying carbon-containing palladium catalyst.
Embodiment 3-2: polypyrrole modifying carbon supported platinum catalyst preparation
Carbon black 1 gram is distributed to is made into suspension-turbid liquid in the chloroform, its mass ratio is 1: 15; Adding the salt acid for adjusting pH value is 3, stirring at room 30min; Mass ratio by carbon black and pyrroles is that 1: 0.3 adding pyrroles stirs 10min, adds a gram PtCl then
2The H that adds 0.1 gram mass behind the stirring at room 10h again
2O
2Behind the stirring at room 10h, be heated to 90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 60min, natural cooling; After filtering with deionized water wash, behind 90 ℃ of dry 6h of vacuum under Ar atmosphere 600 ℃ of insulation 1h heat-treat, make the polypyrrole modifying carbon supported platinum catalyst.
Embodiment 3-3: polypyrrole modifying carbon carries the Au catalyst preparation
Carbon black 1 gram is distributed to is made into suspension-turbid liquid in the chloroform, its mass ratio is 1: 15; Adding the salt acid for adjusting pH value is 2.8, stirring at room 20min; Mass ratio by carbon black and pyrroles is that 1: 0.2 adding pyrroles stirs 8min, adds a gram AuCl then
2The H that adds 0.08 gram mass behind the stirring at room 6h again
2O
2Behind the stirring at room 6h, be heated to 80 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 45min, natural cooling; After filtering with deionized water wash, behind 80 ℃ of dry 10h of vacuum under Ar atmosphere 500 ℃ of insulation 3h heat-treat, make polypyrrole modifying carbon and carry Au catalyst.
Embodiment 4-1: negative electrode preparation
Carbon black 10 gram is distributed to is made into suspension-turbid liquid in the water, its mass ratio is 1: 15; Adding glacial acetic acid adjusting pH value is 3, stirring at room 30min; Mass ratio by carbon black and pyrroles is that 1: 0.3 adding pyrroles stirs 10min, adds a gram PdCl then
2The H that adds 0.1 gram mass behind the stirring at room 3h again
2O
2Behind the stirring at room 10h, be heated to 90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 60min, natural cooling; After filtering with deionized water wash, behind 90 ℃ of dry 6h of vacuum at N
2The following 600 ℃ of insulation 5h of atmosphere heat-treat, and make the polypyrrole modifying carbon-containing palladium catalyst.
With the polytetrafluoroethylene suspension-turbid liquid of polypyrrole modifying carbon-containing palladium catalyst, water, 5wt.%, absolute ethyl alcohol according to 1: 3: 2: 3 mass ratio hybrid modulation form slurry, be coated on the carbon cloth that hydrophobic is handled, naturally dry and obtain negative electrode, the mass ratio that polypyrrole modifying carbon carries palladium and carbon cloth is 1: 50.
Embodiment 4-2: negative electrode preparation
Carbon black 10 gram is distributed to is made into suspension-turbid liquid in the water, its mass ratio is 1: 15; Adding glacial acetic acid adjusting pH value is 2.8, stirring at room 30min; Mass ratio by carbon black and pyrroles is that 1: 0.3 adding pyrroles stirs 10min, adds a gram AuCl then
2The H that adds 0.1 gram mass behind the stirring at room 3h again
2O
2Behind the stirring at room 10h, be heated to 90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 60min, natural cooling; After filtering with deionized water wash, behind 90 ℃ of dry 6h of vacuum at N
2The following 600 ℃ of insulation 5h of atmosphere heat-treat, and make polypyrrole modifying carbon and carry Au catalyst.
Polytetrafluoroethylene suspension-turbid liquid, absolute ethyl alcohol that polypyrrole modifying carbon is carried Au catalyst, water, 5wt.% were according to 1: 3: 7: 6 mass ratio hybrid modulation form slurry, be coated on the carbon paper that hydrophobic is handled, naturally dry and obtain negative electrode, the mass ratio that polypyrrole modifying carbon carries gold and carbon paper is 1: 10.
Embodiment 4-3: negative electrode preparation
Carbon black 10 gram is distributed to is made into suspension-turbid liquid in the water, its mass ratio is 1: 15; Adding the salt acid for adjusting pH value is 2.5, stirring at room 30min; Mass ratio by carbon black and pyrroles is that 1: 0.3 adding pyrroles stirs 10min, adds a gram PtCl then
2The H that adds 0.1 gram mass behind the stirring at room 3h again
2O
2Behind the stirring at room 10h, be heated to 90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 60min, natural cooling; After filtering with deionized water wash, behind 90 ℃ of dry 6h of vacuum at N
2The following 600 ℃ of insulation 5h of atmosphere heat-treat, and make the polypyrrole modifying carbon supported platinum catalyst.
Polytetrafluoroethylene suspension-turbid liquid, absolute ethyl alcohol that polypyrrole modifying carbon is carried Au catalyst, water, 5wt.% were according to 1: 3: 7: 6 mass ratio hybrid modulation form slurry, be coated on the carbon cloth that hydrophobic is handled, naturally dry and obtain negative electrode, the mass ratio that polypyrrole modifying carbon carries platinum and carbon cloth is 1: 100.
Embodiment 5: the direct dimethyl ether fuel battery of anion-exchange membrane
The polypyrrole modifying carbon that obtains is carried the poly-vinyl alcohol solution of Pt-Ru catalyst, water, 5wt.% and absolute ethyl alcohol according to 1: 3: 2: 3 mass ratio hybrid modulation form slurry, be coated on the nickel foam of hydrophilic treated, naturally make anode after drying, the mass ratio that polypyrrole modifying carbon carries Pt-Ru catalyst and nickel foam is 1: 100.
By anion-exchange membrane the negative electrode that above-mentioned anode and embodiment 4-1 obtain is separated, selecting concentration is 1M L
-1NaOH and 0.5M L
-1Na
2SO
4Solution charges in the nickel foam of anode catalyst carrier, by the fuel cell that is assembled into shown in Figure 5.The polarization curve of the negative electrode of this direct dimethyl ether fuel battery and anode as shown in Figure 6 under 80 ℃.
Embodiment 6: the direct dimethyl ether fuel battery of cation-exchange membrane
Polypyrrole modifying carbon is carried the polytetrafluoroethylene suspension-turbid liquid of Au catalyst, water, 5wt.% and absolute ethyl alcohol according to 1: 3: 5: 5 mass ratio hybrid modulation form slurry, be coated on the carbon paper that hydrophobic is handled, naturally dry and obtain negative electrode, the mass ratio that polypyrrole modifying carbon carries gold and carbon paper is 1: 50.The anode, the alkali lye that charges into anode catalyst carrier and the above-mentioned negative electrode that embodiment 2-1 are obtained by cation-exchange membrane separate, and selecting concentration is 1M L
-1NaOH and 0.5M L
-1Na
2SO
4Solution charges in the nickel foam of anode catalyst carrier, by the fuel cell that is assembled into shown in Figure 5.The power generation performance of this direct dimethyl ether fuel battery as shown in Figure 7 under 80 ℃.
Embodiment 7:KOH is the direct dimethyl ether fuel battery of the anion-exchange membrane of anolyte
The negative electrode that anode that embodiment 2-2 is obtained by anion-exchange membrane and embodiment 4-2 obtain separates, and selection concentration is 6ML
-1KOH solution charge in the nickel foam of anode catalyst carrier, constituting KOH is the direct dimethyl ether fuel battery of anolyte, 80 ℃ down the maximum energy-density of these direct dimethyl ether fuel batteries reach 80mW cm
-2
Embodiment 8:KOH is the direct dimethyl ether fuel battery of the cation-exchange membrane of anolyte
The negative electrode that anode that embodiment 2-2 is obtained by cation-exchange membrane and embodiment 4-3 obtain separates, and selection concentration is 3ML
-1KOH solution charge in the nickel foam of anode catalyst carrier, constituting KOH is the direct dimethyl ether fuel battery of anolyte, 80 ℃ down the maximum energy-density of these direct dimethyl ether fuel batteries reach 92mW cm
-2
Embodiment 9: the fuel cell among the present invention has following structural configuration:
Fuel cell has the following structure of arranging successively at horizontal direction: plate 1, anode catalyst carrier (nickel foam 16), anode catalyst 3, barrier film 10, cathod catalyst 5, cathode catalysis agent carrier 6 and cathode plate 8; Sealing is all realized with sealing ring in the two ends up and down of fuel cell, and its negative terminal 12 is drawn by nickel foam 16, and positive terminal 13 is drawn by cathode plate 8; Establish gas of dimethyl ether inlet 15 in nickel foam 16 bottoms, tail gas outlet 14 is established on its top; Described cathode catalysis agent carrier 6 is carbon paper or carbon cloths of handling through hydrophobic, and described cathode plate 8 has air flue 7; Described anode catalyst carrier is the nickel foam through hydrophilic treated, and it is electrolyte that anode catalyst carrier contains alkaline dimethyl ether solution.Anode catalyst carrier also can be selected carbon paper or the carbon cloth through hydrophilic treated for use, and negative terminal 12 changed by plate 1 and drew this moment.
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.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 (5)
1. alkaline direct dimethyl ether fuel cell, cut off anode and negative electrode with cation-exchange membrane or anion-exchange membrane as barrier film, the alkaline dimethyl ether solution that contains with anode catalyst carrier is electrolyte, it is characterized in that described alkaline dimethyl ether solution is that dimethyl ether is saturated, NaOH or KOH concentration are the aqueous solution of 1～6 mol.
2. alkaline direct dimethyl ether fuel cell according to claim 1, it is characterized in that described fuel cell has the following structure of arranging successively at horizontal direction: plate, anode catalyst carrier, anode catalyst, barrier film, cathod catalyst, cathode catalysis agent carrier and cathode plate; Sealing is all realized with sealing ring in the two ends up and down of fuel cell, and its negative terminal is drawn by anode catalyst carrier, and positive terminal is drawn by cathode plate; Establish the gas of dimethyl ether inlet in the anode catalyst carrier bottom, the tail gas outlet is established on its top; Described cathode catalysis agent carrier is carbon paper or the carbon cloth of handling through hydrophobic, and described cathode plate has air flue; Described anode catalyst carrier is carbon paper, carbon cloth or the nickel foam through hydrophilic treated, and filling contains the NaOH of dimethyl ether or the KOH aqueous solution as electrolyte.
3. alkaline direct dimethyl ether fuel cell according to claim 1 is characterized in that, as cathod catalyst, its negative electrode makes by following manner described fuel cell with the polypyrrole modifying carbon supported noble metal catalyst:
(1) preparation polypyrrole modifying carbon supported noble metal:
Carbon black is distributed in water, methyl alcohol or the chloroform is made into suspension-turbid liquid, its mass ratio is 1: 15; Adding glacial acetic acid or salt acid for adjusting pH value is 2.5～3, stirring at room 10～30min; Mass ratio by carbon black and pyrroles is that 1: 0.05～0.3 adding pyrroles stirs 5～10min, adds the chloride of gram Pt, Pd or Au then; The H that adds 0.05～0.1 gram mass behind stirring at room 3～10h again
2O
2Behind stirring at room 3～10h, be heated to 70～90 ℃; Slowly adding 300ml concentration is 0.1ML
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 30～60min, natural cooling; After filtering with deionized water wash, behind 70～90 ℃ of drying 6～12h of vacuum at Ar or N
2Inert atmosphere under 300～600 ℃ the insulation 1～5h heat-treat, make corresponding polypyrrole modifying carbon supported noble metal catalyst;
(2) with the polytetrafluoroethylene suspension-turbid liquid of polypyrrole modifying carbon supported noble metal catalyst, water, 5wt.%, absolute ethyl alcohol according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation form slurry, be coated on carbon paper or carbon cloth that hydrophobic is handled, naturally dry and get final product, the mass ratio of polypyrrole modifying carbon supported noble metal catalyst and carbon paper or carbon cloth is 1: 10～100.
4. alkaline direct dimethyl ether fuel cell according to claim 1 is characterized in that, this fuel cell carries the Pt-Ru catalyst as anode catalyst with polypyrrole modifying carbon, and the mass ratio of Pt-Ru catalyst and polypyrrole modifying carbon carrier is 1: 1～9; The mass ratio of Pt and Ru is 1: 0.5～1 in the catalyst; Described anode catalyst makes by following manner:
Carbon black is distributed in water, methyl alcohol or the chloroform is made into suspension-turbid liquid, its mass ratio is 1: 15; Adding glacial acetic acid or salt acid for adjusting pH value is 2.5～3, stirring at room 10～30min; Mass ratio by carbon black and pyrroles is that 1: 0.05～0.3 adding pyrroles stirs 5～10min, and the mass ratio that adds Pt and Ru then is 1: 0.5～1 PtCl
2And RuCl
2The H that adds 0.05～0.1 gram mass behind stirring at room 3～10h again
2O
2Behind stirring at room 3～10h, be heated to 70～90 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 30～60min, natural cooling; After filtering with deionized water wash, behind 70～90 ℃ of drying 6～12h of vacuum at Ar or N
2Inert atmosphere under 300～600 ℃ the insulation 1～5h heat-treat, make polypyrrole modifying carbon and carry the Pt-Ru catalyst.
5. alkaline direct dimethyl ether fuel cell according to claim 4, it is characterized in that, the anode of this fuel cell makes by following manner: carry the Pt-Ru catalyst by described polypyrrole modifying carbon: the poly-vinyl alcohol solution of water: 5wt.% or perfluor sulfoacid resin solution: the mass ratio of absolute ethyl alcohol is 1: 3: 2～7: 3～6 hybrid modulation slurries, be coated to then on carbon paper, carbon cloth or the nickel foam through hydrophilic treated, naturally dry and get final product, the mass ratio that polypyrrole modifying carbon carries Pt-Ru catalyst and carbon paper, carbon cloth or nickel foam is 1: 10～100.
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Cited By (4)
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| CN104979576A (en) * | 2014-04-04 | 2015-10-14 | 陈家骏 | Methanol battery |
| CN109888321A (en) * | 2019-01-21 | 2019-06-14 | 西安交通大学 | Fuel cascade utilization feed separation transmits fuel cell and its working method |
| CN110534753A (en) * | 2019-08-22 | 2019-12-03 | 浙江大学 | The glucose fuel cell for having homogeneous auxiliary catalysis |
| CN112436167A (en) * | 2020-11-17 | 2021-03-02 | 中国科学院兰州化学物理研究所 | Direct type polyether compound fuel cell and system |
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| CN1457112A (en) * | 2003-06-06 | 2003-11-19 | 南开大学 | Alkaline fuel battery with hydrogen storage alloy as electric catalyst |
| CN1933228A (en) * | 2006-09-28 | 2007-03-21 | 哈尔滨工业大学 | Self-heating direct dimethyl ether fuel battery system |
| US20080070094A1 (en) * | 2006-06-20 | 2008-03-20 | Lg Chem, Ltd. | Organic/inorganic composite electrolyte membranes using zeolite and fuel cell comprising the same |
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| JP2002373686A (en) * | 2001-06-14 | 2002-12-26 | Mitsubishi Electric Corp | Temperature and humidity regulating device and temperature and humidity regulating method for fuel cell reactant gas |
| CN1457112A (en) * | 2003-06-06 | 2003-11-19 | 南开大学 | Alkaline fuel battery with hydrogen storage alloy as electric catalyst |
| US20080070094A1 (en) * | 2006-06-20 | 2008-03-20 | Lg Chem, Ltd. | Organic/inorganic composite electrolyte membranes using zeolite and fuel cell comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104979576A (en) * | 2014-04-04 | 2015-10-14 | 陈家骏 | Methanol battery |
| CN109888321A (en) * | 2019-01-21 | 2019-06-14 | 西安交通大学 | Fuel cascade utilization feed separation transmits fuel cell and its working method |
| CN110534753A (en) * | 2019-08-22 | 2019-12-03 | 浙江大学 | The glucose fuel cell for having homogeneous auxiliary catalysis |
| CN110534753B (en) * | 2019-08-22 | 2021-02-12 | 浙江大学 | Glucose fuel cell with homogeneous auxiliary catalysis |
| CN112436167A (en) * | 2020-11-17 | 2021-03-02 | 中国科学院兰州化学物理研究所 | Direct type polyether compound fuel cell and system |
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