CN102394306A - Membrane electrode and fuel cell therewith - Google Patents
Membrane electrode and fuel cell therewith Download PDFInfo
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- CN102394306A CN102394306A CN2011103679504A CN201110367950A CN102394306A CN 102394306 A CN102394306 A CN 102394306A CN 2011103679504 A CN2011103679504 A CN 2011103679504A CN 201110367950 A CN201110367950 A CN 201110367950A CN 102394306 A CN102394306 A CN 102394306A
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- electrode
- carbon nanotube
- long line
- nanotube long
- catalyst
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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
Abstract
The invention relates to a membrane electrode. The membrane electrode comprises a proton exchange membrane, a first electrode arranged on one surface of the proton exchange membrane, and a second electrode arranged on the opposite surface of the proton exchange membrane, wherein at least one of the first electrode and the second electrode comprises at least one carbon nanotube yarn composite structure which comprises a carbon nanotube yarn and a catalyst distributed in the carbon nanotube yarn, and the carbon nanotube yarn comprises a plurality of end-to-end carbon nanotubes which are arranged along the length direction of the carbon nanotube yarn in a preferable orientation mode. The invention also provides a fuel cell with the membrane electrode. The membrane electrode and the fuel cell of the invention have high reaction activities and allow the utilization rate of the catalyst to be improved.
Description
Technical field
The present invention relates to a kind of membrane electrode and adopt the fuel cell of this membrane electrode, relate in particular to a kind of based on CNT membrane electrode and adopt the fuel cell of this membrane electrode.
Background technology
Fuel cell is a kind of electrochemical generating unit that fuel and oxidant gas is converted into electric energy; The fields such as military and national defense and civilian electric power, automobile, communication that are widely used in (see also; Recent advances in fuel cell technology and its application; Journal of Power Sources, V100, P60-66 (2001)).
Usually; A fuel cell mainly comprises membrane electrode (Membrane Electrode Assembly is called for short MEA), baffler (Flow Field Plate; Be called for short FFP); Collector plate (Current Collector Plate is called for short CCP) and relevant accessory, as: air blast, valve, pipeline etc.
Membrane electrode (MEA) is the core component of cell of fuel cell, and it normally is made up of a PEM (Proton Exchange Membrane) and the electrodes that are separately positioned on PEM two surface.Wherein, electrode comprises Catalytic Layer (Catalyst Layer) and gas diffusion layers (Gas Diffusion Layer is called for short GDL) again, and Catalytic Layer is arranged between gas diffusion layers and the PEM.Proton exchange membrane material is selected from perfluorinated sulfonic acid, polystyrolsulfon acid, polytrifluorostyrene sulfonic acid, phenolic resins sulfonic acid or hydrocarbon.Catalytic Layer includes catalyst material (be generally noble metal granule, as: platinum, gold or ruthenium etc.) and carrier thereof (be generally carbon granule, as: graphite, carbon black, carbon fiber or CNT).Gas diffusion layers mainly is made up of carbon fiber paper.
Yet; Not enough below the membrane electrode of fuel cell of the prior art exists: the first, owing to gas diffusion layers mainly is made up of carbon fiber paper, on the one hand; Contain a large amount of mixed and disorderly carbon fibers that distribute in this carbon fiber paper; Cause carbon fiber paper mesopore structure distribution inhomogeneous, and specific area is little, thereby has influenced the uniformity of reacting gas diffusion; On the other hand, carbon fiber paper resistivity is big, has restricted the transmission of reacting the necessary electronics and the electronics of reaction generation, thereby has directly influenced the reactivity of membrane electrode.The second, because each electrode comprises that a gas diffusion layers and is formed at the Catalytic Layer of gaseous diffusion laminar surface, on the one hand, this structure makes membrane electrode have bigger thickness, and has increased film-electrode gas diffusion layer and catalysis
Contact resistance between the layer is unfavorable for electrical conductivity; On the other hand, the catalyst in the Catalytic Layer and the contact area of reacting gas are little, have limited the utilance of catalyst.
In view of this, necessary a kind of high reaction activity and high that has is provided, and can improves membrane electrode and the fuel cell that adopts this membrane electrode of the utilance of catalyst.
Summary of the invention
A kind of membrane electrode; It comprises: a PEM; One first electrode and one second electrode, said first electrode and second electrode are arranged at two facing surfaces of this PEM respectively, wherein; At least one electrode in said first electrode and second electrode comprises at least one carbon nanotube long line composite construction; And this carbon nanotube long line composite construction comprises carbon nanotube long line and catalyst, and catalyst distribution is in this carbon nanotube long line, and said carbon nanotube long line comprises a plurality of CNTs that join end to end and be arranged of preferred orient along this carbon nanotube long line length direction.
A kind of fuel cell, it comprises: a PEM; One first electrode and one second electrode, said first electrode and second electrode are arranged at two facing surfaces of this PEM respectively; One first baffler and one second baffler are arranged at first electrode and second electrode surface away from PEM respectively; And one first air feed and air extractor and one second air feed and air extractor be connected with first baffler and second baffler respectively; It is characterized in that; At least one electrode in said first electrode and second electrode comprises at least one carbon nanotube long line composite construction; And this carbon nanotube long line composite construction comprises carbon nanotube long line and catalyst; Catalyst distribution is in this carbon nanotube long line, and said carbon nanotube long line comprises a plurality of CNTs that join end to end and be arranged of preferred orient along this carbon nanotube long line length direction.
Compared to prior art; Said membrane electrode has the following advantages: first; At least one the electrodes use carbon nanotube long line in said first electrode and second electrode and the composite construction of catalyst; So avoided the contact resistance between the diffusion layer and catalyst layer in the prior art, helped reacting the conduction of the electronics that necessary electronics and reaction generate.The second, carbon nanotube long line has great specific area, so, adopt this carbon nanotube long line can be effective and catalyst-loaded uniformly, make catalyst and hydrogen fuel or oxidant gas have bigger contact area, improved the utilance of catalyst.The 3rd; Because the resistivity of CNT itself will be lower than the resistivity of carbon fiber; So adopt the resistivity of electrode of composite construction of this carbon nanotube long line and catalyst low; Can effectively conduct necessary electronics of reaction and the electronics that reaction generates, help to improve the reactivity of membrane electrode.
Description of drawings
Fig. 1 is the structural representation of the membrane electrode of present technique scheme implementation example.
The surperficial vapor deposition that Fig. 2 provides for present technique scheme implementation example has the partial sweep electromicroscopic photograph of the carbon nano-tube film behind the platinum layer.
Fig. 3 is the structural representation of the fuel cell of present technique scheme implementation example.
Embodiment
Below will combine accompanying drawing that the present technique scheme is done further to specify.
See also Fig. 1, present technique scheme implementation example provides a kind of membrane electrode 200, and it comprises: a PEM 202, one first electrodes 204, one second electrodes 206.Said first electrode 204 and second electrode 206 are separately positioned on two facing surfaces of this PEM 202.At least one electrode in said first electrode 204 and second electrode 206 comprises at least one carbon nanotube long line composite construction, and this carbon nanotube long line composite construction comprises carbon nanotube long line and catalyst, and catalyst distribution is in this carbon nanotube long line.
Said carbon nanotube long line comprise a plurality of join end to end and along this carbon nanotube long line axially/CNT that length direction is arranged of preferred orient.Particularly, in this carbon nanotube long line CNT along this carbon nanotube long line axially/length direction be arranged in parallel or in the shape of a spiral shape arrange.Length of carbon nanotube is basic identical in this carbon nanotube long line, and combines closely through Van der Waals force between the adjacent CNT.Said CNT comprises one or more in SWCN, double-walled carbon nano-tube and the multi-walled carbon nano-tubes.The diameter of said SWCN is 0.5 nanometer ~ 10 nanometers, and the diameter of double-walled carbon nano-tube is 1.0 nanometers ~ 15 nanometers, and the diameter of multi-walled carbon nano-tubes is 1.5 nanometers ~ 50 nanometers.The length of this CNT is greater than 100 microns.In the present embodiment, preferably, the length of CNT is 200 ~ 900 microns.
After said carbon nanotube long line can obtain a carbon nano-tube film through the carbon nano pipe array that stretches, through mechanical external force shrink process (surface tension effects of organic solvent volatilization); Reversing spinning handles or curls and obtain.The diameter of said carbon nanotube long line is 1 micron ~ 1 millimeter, and its length is not limit, and can make according to the actual requirements.Before the carbon nano-tube film that pulls is prepared into carbon nanotube long line, earlier catalyst is deposited to the carbon nano-tube film surface through physics or chemical method, again through mechanical external force shrink process (surface tension effects of organic solvent volatilization); Reverse the spinning processing or curl and to obtain the composite construction of carbon nanotube long line and catalyst.See also Fig. 2, catalyst is uniformly distributed in the carbon nano tube surface of carbon nano-tube film.So in this carbon nanotube long line composite construction, catalyst is uniformly distributed in the carbon nano tube surface in the carbon nanotube long line.
The material of said catalyst is not limit, and can be noble metal granule, as: the mixture of a kind of or its combination in any in platinum, gold, the ruthenium.The diameter dimension of this metallic particles is 1 ~ 10 nanometer.The loading of said noble metal catalyst is lower than 0.5mg/cm
2, and be uniformly distributed in the carbon nano tube surface of carbon nanotube long line.In the present embodiment, noble metal catalyst is a platinum.
Said carbon nanotube long line composite construction is fixed in the surface of PEM 202 through the method for self viscosity, binding agent or hot pressing.When said electrode comprises a plurality of carbon nanotube long line composite construction; A plurality of carbon nanotube long line composite constructions can be arranged in parallel or be arranged in a crossed manner in the surface of PEM 202, and can not have gap setting or setting at interval between the carbon nanotube long line composite construction.When a plurality of carbon nanotube long line composite constructions intersect and be provided with at interval, form between the said carbon nanotube long line composite construction a plurality of evenly and the micropore of regular distribution, and this micropore size is less than 1 micron.
Be appreciated that; When at least one electrode in said first electrode 204 and second electrode 206 comprises at least one carbon nanotube long line composite construction; The structure of another electrode is not limit; Can comprise that a diffusion layer and a catalyst layer are arranged on this diffusion layer, and this catalyst layer is arranged between PEM and the diffusion layer.Said diffusion layer can be a carbon fiber paper or carbon nanotube layer.This catalyst layer includes precious metal catalyst agent material and carrier thereof (be generally carbon granule, as: graphite, carbon black, carbon fiber or CNT).In the present embodiment, preferably, said first electrode 204 and second electrode 206 include a plurality of carbon nanotube long line composite constructions.And this parallel no gap of a plurality of carbon nanotube long line composite constructions is arranged at two facing surfaces of PEM 202.
The material of said PEM 202 is perfluorinated sulfonic acid, polystyrolsulfon acid, polytrifluorostyrene sulfonic acid, phenolic resins sulfonic acid or hydrocarbon.In the present embodiment, PEM 202 materials are perfluorinated sulfonic acid.
Said membrane electrode 200 has the following advantages: first; Said first electrode 204 and second electrode 206 all adopt the composite construction of carbon nanotube long line and catalyst; So avoided the contact resistance between the diffusion layer and catalyst layer in the prior art, helped reacting the conduction of the electronics that necessary electronics and reaction generate.The second, carbon nanotube long line has great specific area, so, adopt this carbon nanotube long line can be effective and catalyst-loaded uniformly, make catalyst and hydrogen fuel or oxidant gas have bigger contact area, improved the utilance of catalyst.The 3rd; Because the resistivity of CNT itself will be lower than the resistivity of carbon fiber; So adopt the resistivity of electrode of composite construction of this carbon nanotube long line and catalyst low; Can effectively conduct necessary electronics of reaction and the electronics that reaction generates, help to improve the reactivity of membrane electrode.The 4th; Said first electrode 204 and second electrode 206 all adopt the composite construction of carbon nanotube long line and catalyst; This carbon nanotube long line has collected current and effect catalyst-loaded and diffusible hydrogen fuel or oxidant gas simultaneously, and is simple in structure, easy to use.
See also Fig. 3; Present technique scheme implementation example also further provides a fuel cell 20; It comprises: a membrane electrode 200; One first baffler 208a and one second baffler 208b, one first collector plate 216a and one second collector plate 216b, and one first air feed and air extractor 210a and one second air feed and air extractor 210b.
The structure of said membrane electrode 200 as previously mentioned.That is, said first electrode 204 and second electrode 206 include the composite construction of a plurality of carbon nanotube long line and noble metal catalyst particle.And this parallel no gap of a plurality of carbon nanotube long line composite constructions is arranged at two facing surfaces of PEM 202.
The said first baffler 208a and the second baffler 208b are arranged at first electrode 204 and second electrode 206 surface away from PEM 202 respectively.The surface near PEM 202 at the first baffler 208a and the second baffler 208b has one or more guiding gutter 212, is used to conduct fuel gas, oxidant gas and reaction product water.This first baffler 208a and the second baffler 208b adopt metal or conductive carbon material to make.
The said first collector plate 216a and the second collector plate 216b adopt electric conducting material to make, and are arranged at the surface away from PEM 202 of the first baffler 208a and the second baffler 208b respectively, are used to collect and conduct the electronics that reaction produces.Be appreciated that in the present embodiment, because carbon nanotube long line itself has good electrical conductivity, can be used for collected current, so but this first collector plate 216a and the second collector plate 216b are a choice structure.
Said first air feed and air extractor 210a and second air feed and air extractor 210b comprise air blast, pipeline, valve etc. (not indicating among the figure).Air blast links to each other with the first baffler 208a and the second baffler 208b respectively through pipeline, is used for to fuel cell 20 fuel gas and oxidant gas being provided.In the present embodiment, fuel gas is a hydrogen, and oxidant gas is purity oxygen or oxygen containing air.Wherein, second electrode 206 near the oxidant gas input in the fuel cell 20 is called negative electrode, is called anode near first electrode 204 of fuel gas input.
When above-mentioned fuel cell 20 is worked, utilize its air feed and air extractor 210 to feed fuel gas (hydrogen) and oxidant gas (purity oxygen or oxygen containing air) to membrane electrode 200 respectively through baffler 208.Wherein, hydrogen arrives anode through guiding gutter 212.Under the effect of catalyst, following reaction: H takes place in hydrogen
2→ 2H
++ 2e.The proton that reaction generates passes PEM 202 and arrives negative electrode, and the electronics that reaction generates then arrives negative electrode through external circuit.
At fuel cell 20 other ends, oxygen gets into negative electrode, and simultaneously, electronics then arrives negative electrode through external circuit.Under the effect of catalyst, following reaction: 1/2O takes place in oxygen and proton and electronics
2+ 2H
++ 2e → H
2O.The water that reaction generates is then discharged fuel cell 20 through second electrode 206 and baffler 208.In this process, can form certain electrical potential difference between first electrode 204 and second electrode 206, when external circuit inserts a load 214, will form electric current.
In addition, those skilled in the art also can do other variations in spirit of the present invention, and certainly, these all should be included within the present invention's scope required for protection according to the variation that the present invention's spirit is done.
Claims (12)
1. membrane electrode; It comprises: a PEM; One first electrode and one second electrode, said first electrode and second electrode are arranged at two facing surfaces of this PEM respectively, it is characterized in that; At least one electrode in said first electrode and second electrode comprises at least one carbon nanotube long line composite construction; And this carbon nanotube long line composite construction comprises carbon nanotube long line and catalyst, and catalyst distribution is in this carbon nanotube long line, and said carbon nanotube long line comprises a plurality of CNTs that join end to end and be arranged of preferred orient along this carbon nanotube long line length direction.
2. membrane electrode as claimed in claim 1 is characterized in that, at least one electrode in said first electrode and second electrode comprises that a plurality of carbon nanotube long line composite constructions are arranged in parallel or be arranged in a crossed manner in the surface of this PEM.
3. membrane electrode as claimed in claim 1 is characterized in that, the diameter of said carbon nanotube long line composite construction is 1 micron ~ 1 millimeter.
4. membrane electrode as claimed in claim 1 is characterized in that, combines closely through Van der Waals force between the adjacent CNT in the said carbon nanotube long line composite construction.
5. membrane electrode as claimed in claim 1 is characterized in that, the length of said CNT is 200 ~ 900 microns, and diameter is less than 50 nanometers.
6. membrane electrode as claimed in claim 1 is characterized in that said catalyst is uniformly distributed in the carbon nano tube surface in this carbon nanotube long line.
7. membrane electrode as claimed in claim 1 is characterized in that, said catalyst is a noble metal granule, and its material is the mixture of a kind of or its combination in any in platinum, gold or the ruthenium.
8. membrane electrode as claimed in claim 1 is characterized in that, said first electrode and second electrode include said at least one carbon nanotube long line composite construction.
9. membrane electrode as claimed in claim 1 is characterized in that, said first electrode and second electrode are formed by said carbon nanotube long line composite construction.
10. fuel cell, it comprises: a PEM; One first electrode and one second electrode, said first electrode and second electrode are arranged at two facing surfaces of this PEM respectively; One first baffler and one second baffler are arranged at first electrode and second electrode surface away from PEM respectively; And one first air feed and air extractor and one second air feed and air extractor be connected with first baffler and second baffler respectively; It is characterized in that; At least one electrode in said first electrode and second electrode comprises at least one carbon nanotube long line composite construction; And this carbon nanotube long line composite construction comprises carbon nanotube long line and catalyst; Catalyst distribution is in this carbon nanotube long line, and said carbon nanotube long line comprises a plurality of CNTs that join end to end and be arranged of preferred orient along this carbon nanotube long line length direction.
11. fuel cell as claimed in claim 10 is characterized in that, said first electrode and second electrode include said at least one carbon nanotube long line composite construction.
12. a fuel cell, it comprises: like each described membrane electrode of claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103679504A CN102394306B (en) | 2008-07-25 | 2008-07-25 | Membrane electrode and fuel cell therewith |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103679504A CN102394306B (en) | 2008-07-25 | 2008-07-25 | Membrane electrode and fuel cell therewith |
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| CN2008101425249A Division CN101635362B (en) | 2007-11-02 | 2008-07-25 | Membrane electrode and fuel cell adopting same |
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| CN102394306A true CN102394306A (en) | 2012-03-28 |
| CN102394306B CN102394306B (en) | 2013-04-24 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050142428A1 (en) * | 2003-12-26 | 2005-06-30 | Hitachi Maxell, Ltd. | Fuel cell and membrane electrode assembly |
| JP2008059841A (en) * | 2006-08-30 | 2008-03-13 | Toyota Motor Corp | Fuel cell and manufacturing method of fuel cell |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050142428A1 (en) * | 2003-12-26 | 2005-06-30 | Hitachi Maxell, Ltd. | Fuel cell and membrane electrode assembly |
| JP2008059841A (en) * | 2006-08-30 | 2008-03-13 | Toyota Motor Corp | Fuel cell and manufacturing method of fuel cell |
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| CN102394306B (en) | 2013-04-24 |
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