CN103682372A - Micro membrane-free fuel cell with carbon-nanotube three-dimensional electrodes and preparation method thereof - Google Patents
Micro membrane-free fuel cell with carbon-nanotube three-dimensional electrodes and preparation method thereof Download PDFInfo
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- CN103682372A CN103682372A CN201310631030.8A CN201310631030A CN103682372A CN 103682372 A CN103682372 A CN 103682372A CN 201310631030 A CN201310631030 A CN 201310631030A CN 103682372 A CN103682372 A CN 103682372A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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 belongs to the technical field of fuel cells, and particularly relates to a micro membrane-free fuel cell with carbon-nanotube three-dimensional electrodes and a preparation method thereof. A metal electrode lead is arranged on the surface of a substrate material of the micro membrane-free fuel cell, and a plurality of carbon-nanotube three-dimensional electrodes and a plurality of carbon-nanotube diversion screen plates are grown on the metal electrode lead in a positioned mode. Catalysts are loaded on the carbon-nanotube three-dimensional electrodes. The substrate material and a cover slip with a groove are bonded and packaged to obtain the micro membrane-free fuel cell. The micro membrane-free fuel cell utilizes the carbon-nanotube three-dimensional electrodes loaded with the catalysts so as to increase the contact area of a working substance and the electrodes, the perturbation action of the three-dimensional electrodes on laminar substances strengthens the local diffusion of substances, and reactants near an electrode consumption boundary layer can obtain sustained and effective supplement, so that the cell has a high power density.
Description
Technical field
The invention belongs to fuel cell technology field, be specifically related to the miniature without membrane cell and preparation method thereof of a kind of carbon nanotubes stereo electrod.
Background technology
Along with the development of Mobile portable equipment is with universal, energy device is in the past cannot meet the mankind's requirement, and demand high for energy density and the energy device that size is small is extremely urgent.Miniature without a series of advantages such as membrane cell are simple in structure owing to having, efficient, clean, practical, simultaneously owing to there is no proton exchange membrane, manufacture craft is simple, with low cost.
In fuel cell, all redox reactions are all carried out based on plane electrode surface, and because reaction is almost only carried out near electrode, the contact area of electrode and operation material is less.It is plane that the existing miniature electrode without membrane cell is generally strip, be distributed in the both sides of microchannel, fuel and oxidant flow through and redox reaction occur at anode and cathode surface respectively, this two dimensional surface electrode effectively utilize area little, fuel availability and power density are low.
Summary of the invention
The present invention, for solution prior art midplane electrode battery fuel availability is low and the low problem of power density, provides the miniature without membrane cell and preparation method thereof of a kind of carbon nanotubes stereo electrod.
A kind of carbon nanotubes stereo electrod miniature without membrane cell, on the described miniature baseplate material surface without membrane cell, there is metal electrode lead-in wire, the upper located growth of described metal electrode lead-in wire has a plurality of carbon nano-tube stereo electrods and a plurality of carbon nano-tube water conservancy diversion web plate, on described carbon nano-tube stereo electrod, load has catalyst, and described baseplate material is with miniature without membrane cell containing obtaining after the encapsulation of fluted cover plate bonding.
In such scheme, described baseplate material is silicon chip or sheet glass.
In such scheme, described metal electrode lead-in wire is chromium-Jin double-layer metal film contact conductor.
In such scheme, described carbon nano-tube stereo electrod is to consist of numerous carbon nano-tube fasciculations, and described in each, the area of carbon nano-tube stereo electrod is 20～10000 μ m
2, the height of stereo electrod is 20～200 μ m; Spacing between carbon nano-tube stereo electrod and carbon nano-tube stereo electrod is 20～100 μ m; Described carbon nano-tube water conservancy diversion web plate is comprised of carbon nano-tube, is linear, and the width of each water conservancy diversion web plate is 10～50 μ m, and height is 20～200 μ m, and the spacing between water conservancy diversion web plate and water conservancy diversion web plate is 20～100 μ m.
In such scheme, described catalyst is metallic catalyst or the alloy catalyst of platinum, palladium, copper, gold, silver.
In such scheme, the degree of depth of described groove is consistent with the height of carbon nanotube electrode and carbon nano-tube water conservancy diversion web plate, and the length and width size of described groove is consistent with the upper carbon nanotube electrode of located growth of metal electrode lead-in wire and the area size of carbon nano-tube water conservancy diversion web plate.
A miniature method without membrane cell of preparing above-mentioned carbon nanotubes stereo electrod, comprises the steps:
(1) on baseplate material, prepare metal electrode lead-in wire;
(2) adopt micro-contact-printing, printing is for the catalyst pulp of catalyzed carbon nanotube growth on above-mentioned metal electrode lead-in wire to utilize PDMS Transfer seal, and the printing position of this catalyst pulp on metal electrode lead-in wire be the determining positions on metal electrode lead-in wire by carbon nano-tube stereo electrod and carbon nano-tube water conservancy diversion web plate;
(3) on the above-mentioned metal electrode that is printed with catalyst pulp goes between, adopt chemical gaseous phase deposition legal position carbon nano-tube stereo electrod and carbon nano-tube water conservancy diversion web plate;
(4) on above-mentioned carbon nano-tube stereo electrod load for the catalyst of oxygenated fuel and oxygen reduction agent;
(5) by after the cover plate containing groove and the encapsulation of baseplate material bonding, obtain the miniature without membrane cell of carbon nanotubes stereo electrod.
In such scheme, the preparation method of described metal electrode lead-in wire is: first on baseplate material, prepare metal film; Then in described metallic film surface, apply one deck photoresist; Again described photoresist is carried out to photoetching and development treatment, make photoresist remaining on described metal film present required electrode pattern, put it into subsequently in etching liquid and carry out etching, obtain required electrode shape; Described photoresist after last carbonization etching, puts into high temperature furnace by the photoresist after described etching and heat-treats.
Aforesaid substrate material is silicon chip or glass, and above-mentioned metal film is chromium-Jin double-layer metal film, and above-mentioned etching liquid is chromium etching liquid and golden etching liquid, and the above-mentioned method of preparing metal film is sputtering method, magnetron sputtering method or thermal evaporation plating method; Particularly, the technological parameter that described magnetron sputtering method is prepared described metal film is: chamber pressure is 0.5～0.6Pa, and sputtering power is 80～100W, and argon gas flow velocity is 10～12cm
2/ min, sputtering time is 2～3min; Adopt even glue method at photoresist described in described metallic film surface coating one deck, the technological parameter of described even glue method is: rotating speed is 700～800rpm, and the time is 6～9s, then is 3500rpm through rotating speed, and the time is 20～30s; Described process of thermal treatment parameter is: the speed with 1～2 ℃/min heats up, under the temperature conditions of 150 ℃, and insulation 0.5h, then the speed with 5 ℃/min is warming up to 350～380 ℃, after insulation 0.5h, cooling with stove.
In such scheme, described catalyst pulp is iron, cobalt, nickel nano-metal particle or iron content, cobalt, the slaine of nickel and the mixture of organic adhesive, the preferred polyethylene glycol of described organic adhesive or polyacrylamide.
In such scheme, described chemical vapour deposition technique is general microwave plasma CVD method, or radio frequency plasma chemical vapour deposition technique, the operating condition of described microwave plasma CVD method is: chamber pressure 0.2～8kPa, carbon source flow 1～5sccm, hydrogen flowing quantity 20～100sccm, time 10～80min, microwave power is 300～800W, the operating condition of described radio frequency plasma chemical vapour deposition technique is: chamber pressure 0.2～8kPa, carbon source flow 1～5sccm, hydrogen flowing quantity 20～100sccm, time 10～80min, radio-frequency power is 200～450W, described carbon source is methane, acetone or ethanol.
In such scheme, described catalyst is general platinum, palladium, copper, gold, silver metallic catalyst or alloy catalyst.
In such scheme, the method of described supported catalyst is: growth is had the baseplate material of carbon nano-tube and water conservancy diversion web plate to be soaked in to contain in the salting liquid of platinum, palladium, copper, gold and/or silver, soak 5～24 hours, taking-up utilizes hydrogen plasma, hydrogen or sodium borohydride reduction after drying, obtain and load on metallic catalyst or the alloy catalyst in carbon nano-tube; Or take metal electrode lead-in wire as negative pole, and baseplate material is placed in to electroplating bath, the salting liquid that contains platinum, palladium, copper, gold and/or silver of take is electroplate liquid, obtains metallic catalyst or the alloy catalyst loading in carbon nano-tube by plating.
Beneficial effect of the present invention: the present invention is miniature without membrane cell, utilize load to have the three-dimensional carbon nano-tube of catalyst as electrode, fuel and oxidant have the stereo electrod generation redox reaction of catalyst with the form of the skimming over load of flowing through respectively, this stereo electrod has improved the contact area of reactive material and electrode significantly, stereo electrod has certain perturbation action near laminar flow electrode simultaneously, the perturbation action of laminar flow material has been strengthened to the local diffusion of material, make can obtain supplementing of continuous and effective near the reactant in consumption of electrode boundary layer, therefore the present invention is miniature has high power density and fuel availability without membrane cell.
Accompanying drawing explanation
Fig. 1 is the miniature preparation flow figure without membrane cell of carbon nanotubes stereo electrod, wherein a is for preparing metal film, b is even glue, c is photoetching, d is that wet etching obtains metal electrode lead-in wire, e～-f utilizes PDMS Transfer seal that the catalyst pulp for the growth of catalytic nanometer carbon pipe is printed on to substrate, and g is for utilizing chemical vapor deposition for carbon nanotubes stereo electrod and water conservancy diversion web plate, and h is cell package; In figure, 1 is baseplate material, and 2 is metal film, and 3 is photoresist, and 4 is mask plate, and 5 is exposure, and 6 is metal electrode lead-in wire, and 7 is PDMS Transfer seal, and 8 is catalyst pulp, and 9 is carbon nano-tube, and 10 is cover plate.
Fig. 2 is fuel cell longitudinal cross-section schematic diagram, and wherein 1 is baseplate material, the chromium layer that 2-1 is metal film, and the gold layer that 2-2 is metal film, 3 is silicon dioxide layer, and 4 is carbon nano-tube stereo electrod, and 5 is carbon nano-tube water conservancy diversion web plate, and 6 is cover plate.
Fig. 3 is fuel cell transverse sectional view, and wherein 1 is carbon nano-tube stereo electrod, and 2 is carbon nano-tube water conservancy diversion web plate.
Embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to example below.
Carbon nanotubes stereo electrod miniature without a membrane cell, prepares by the following method, specifically comprises the steps:
(1) at substrate, prepare metal electrode lead-in wire:
1.1 adopt magnetron sputtering method on the sheet glass cleaning up (substrate), to prepare one deck chromium metal film, this chromium metal film is as the transition zone of metal electrode lead-in wire, the technological parameter of magnetron sputtering method is: chamber pressure 0.6Pa, sputtering power 100W, argon gas flow velocity 12cm
2/ min, sputtering time 2min; Adopt DC sputtering on chromium metal film, to prepare layer of gold metal film, this gold metal film is as the conductive layer of metal electrode lead-in wire, and the technological parameter of direct current sputtering is: chamber pressure 8Pa, operating current 8mA, sputtering time 90s; Complete the preparation of chromium-Jin double-level-metal film;
1.2 utilize sol evenning machine to apply one deck photoresist on chromium-Jin double-level-metal film, and the technological parameter of even glue is: low speed 800rpm left and right, time 6s, high speed 3500rpm, time 30s;
1.3 pairs of photoresists carry out the processing such as photoetching, development, graphical photoresist, make photoresist remaining on chromium-Jin double-level-metal film present required electrode pattern, again it is successively put into golden etching liquid, chromium etching liquid etching, chromium-Jin double-level-metal film that removal manifests, obtains required electrode shape;
1.4 put into high temperature furnace by the sheet glass after above-mentioned operation is processed, carbonization photoresist, technological parameter is: the speed with 1 ℃/min heats up, under the temperature conditions of 150 ℃, insulation 0.5h, then the speed with 5 ℃/min is warming up to 380 ℃, after insulation 0.5h, cooling with stove, obtain chromium-Jin double-level-metal contact conductor.
(2) on chromium-Jin double-level-metal lead-in wire, print the catalyst pulp for catalyzed carbon nanotube growth:
1.1 according to the status requirement (see figure 2) of carbon nano-tube stereo electrod and water conservancy diversion web plate, take PDMS(dimethyl silicone polymer) be material, preparation PDMS seal;
1.2 utilize PDMS Transfer seal that the catalyst pulp of the slaine of cobalt and polyethylene glycol composition is printed on Cr/Au metal lead wire, and the effect of this catalyst pulp is the growth of catalyzed carbon nanotube.
(3) on the above-mentioned chromium-Jin double-level-metal that is printed with catalyst pulp goes between, utilize microwave plasma CVD method, direct growth goes out carbon nano-tube stereo electrod and water conservancy diversion web plate, concrete preparation technology parameter is: chamber pressure 200Pa, microwave power 300W, methane flow 2sccm, hydrogen flowing quantity 90sccm, time 40min; Carbon nano-tube stereo electrod and the water conservancy diversion web plate region gross area are 1.5 * 8cm
2, the high 20 μ m of stereoscopic electric, each carbon nano-tube stereo electrod area is 20 μ m
2, spacing between electrodes is 20 μ m; Each water conservancy diversion web plate width 50 μ m, high 20 μ m, between web plate, spacing is 50 μ m.
(4) substrate of carbon nanotubes and water conservancy diversion web plate is soaked in the solution that contains chloroplatinic acid and copper nitrate, soak 18 hours, taking-up utilizes hydrogen plasma reduction after drying, acquisition loads on the Pt/Cu alloy catalyst in carbon nano-tube, described reducing condition is microwave power 100W, chamber pressure 1kPa, hydrogen flow rate 10sccm.
(5) will contain 1.5 * 8cm
2the sheet glass of groove is placed on above-mentioned substrate, utilizes binding agent by two sheet glass tight bond, has completed cell package.
The miniature battery performance without membrane cell of the carbon nanotubes stereo electrod that the present invention prepares: take methyl alcohol as fuel, hydrogen peroxide be oxidant, the Pt/Cu loading on carbon nanotube electrode of take is anode catalyst, the Pt/Cu loading on carbon nanotube electrode is cathod catalyst, and maximum power density reaches 4.25mW/cm
2, fuel availability is 90%.
Carbon nanotubes stereo electrod miniature without a membrane cell, prepares by the following method, specifically comprises the steps:
(1) at substrate, prepare metal electrode lead-in wire:
1.1 adopt magnetron sputtering method on the silicon chip cleaning up (substrate), to prepare one deck chromium metal film, and the technological parameter of magnetron sputtering method is: chamber pressure 0.5Pa, sputtering power 80W, argon gas flow velocity 10cm
2/ min, sputtering time 3min; Adopt direct current secondary sputtering method on chromium metal film, to prepare layer of gold metal film, this gold metal film is as the conductive layer of metal electrode lead-in wire, and the technological parameter of direct current secondary sputter is: chamber pressure 9Pa, operating current 10mA, sputtering time 80s; Complete the preparation of chromium-Jin double-level-metal film;
1.2 utilize sol evenning machine to apply one deck photoresist on chromium-Jin double-level-metal film, and the technological parameter of even glue is: low speed 700rpm left and right, time 9s, high speed 3500rpm, time 20s;
1.3 pairs of photoresists carry out the processing such as photoetching, development, graphical photoresist, make photoresist remaining on chromium-Jin double-level-metal film present required electrode pattern, again it is successively put into golden etching liquid, chromium etching liquid etching, chromium-Jin double-level-metal film that removal manifests, obtains required electrode shape;
1.4 put into high temperature furnace by the silicon chip after above-mentioned operation is processed, carbonization photoresist, technological parameter is: the speed with 2 ℃/min heats up, under the temperature conditions of 150 ℃, insulation 0.5h, then the speed with 5 ℃/min is warming up to 350 ℃, after insulation 0.5h, cooling with stove, obtain chromium-Jin double-level-metal contact conductor.
(2) on chromium-Jin double-level-metal lead-in wire, print the catalyst pulp for catalyzed carbon nanotube growth:
1.1 according to the status requirement (see figure 2) of carbon nano-tube stereo electrod and water conservancy diversion web plate, take PDMS(dimethyl silicone polymer) be material, preparation PDMS seal;
1.2 utilize PDMS Transfer seal that the catalyst pulp of the slaine of nickel and polyacrylamide composition is printed on to chromium-Jin double-level-metal lead-in wire above, and the effect of this catalyst pulp is the growth of catalyzed carbon nanotube.
(3) on the above-mentioned chromium-Jin double-level-metal that is printed with catalyst pulp goes between, utilize microwave plasma CVD method direct growth to go out carbon nano-tube stereo electrod and water conservancy diversion web plate, preparation technology: chamber pressure 5kPa, microwave power 500W, methane flow 3sccm, hydrogen flowing quantity 80sccm, time 50min; Carbon nano-tube stereo electrod and water conservancy diversion web plate region are 2 * 8cm
2, the high 60 μ m of stereoscopic electric, each carbon nano-tube stereo electrod area is 100 μ m
2, spacing between electrodes is 40 μ m; Each water conservancy diversion web plate width 10 μ m, high 60 μ m, between web plate, spacing is 20 μ m.
(4) adopt electric plating method on above-mentioned carbon nano-tube stereo electrod, to deposit for the Pt/Cu metallic catalyst of oxidized or the Pt metallic catalyst of oxidant reduction; Electroplating Pt/Cu metallic catalyst technological parameter is: and electroplate liquid composition (1% chloroplatinic acid: 1% copper chloride: 0.0025% hydrochloric acid: 0.01% lead acetate), operating voltage 5V, working current density 320mA/cm
2, operating time 8s; Electroplating Pt metallic catalyst technological parameter is: and electroplate liquid composition (1% chloroplatinic acid: 0.0025% hydrochloric acid: 0.01% lead acetate), operating voltage 5V, working current density 300mA/cm
2, operating time 10s.
(5) will contain 2 * 8cm
2the sheet glass of groove is placed on above-mentioned substrate, utilizes binding agent by silicon chip and sheet glass tight bond, has completed cell package.
The miniature battery performance without membrane cell of the carbon nanotubes stereo electrod that the present invention prepares: take methyl alcohol as fuel, hydrogen peroxide be oxidant, the Pt/Cu loading on carbon nanotube electrode of take is anode catalyst, the Pt loading on carbon nanotube electrode is cathod catalyst, and maximum power density reaches 4.52mW/cm
2, fuel availability is 88%.
Carbon nanotubes stereo electrod miniature without a membrane cell, prepares by the following method, specifically comprises the steps:
(1) at substrate, prepare metal electrode lead-in wire: the method for preparing metal electrode lead-in wire with embodiment 2 is identical.
(2) on Cr/Au metal lead wire, print the catalyst pulp for catalyzed carbon nanotube growth:
1.1 according to the status requirement (see figure 2) of carbon nano-tube stereo electrod and water conservancy diversion web plate, take PDMS(dimethyl silicone polymer) be material, preparation PDMS seal;
1.2 utilize PDMS Transfer seal that the catalyst pulp of the slaine of iron and polyethylene glycol composition is printed on Cr/Au metal lead wire, and the effect of this catalyst pulp is the growth of catalyzed carbon nanotube.
(3) on the above-mentioned Cr/Au metal lead wire that is printed with catalyst pulp, utilize radio frequency plasma chemical vapour deposition technique direct growth to go out carbon nano-tube stereo electrod and water conservancy diversion web plate, concrete preparation technology is: chamber pressure 5kPa, radio-frequency power 200W, methane flow 3sccm, hydrogen flowing quantity 80sccm, time 80min, carbon nano-tube stereo electrod and water conservancy diversion web plate region are 2 * 8cm
2, the high 200 μ m of stereoscopic electric, each carbon nano-tube stereo electrod area is 100 μ m
2, spacing between electrodes is 60 μ m; Each water conservancy diversion web plate width 30 μ m, high 200 μ m, between web plate, spacing is 40 μ m.
(4) adopt electric plating method on above-mentioned carbon nano-tube stereo electrod, to deposit for the Pt/Au metallic catalyst of oxidized or the Pt metallic catalyst of oxidant reduction and obtain needed carbon nano-tube stereo electrod; Electroplating Pt/Au metallic catalyst technological parameter is: and electroplate liquid composition (1% chloroplatinic acid: 1% gold chloride: 0.0025% hydrochloric acid: 0.01% lead acetate), operating voltage 5V, working current density 320mA/cm
2, operating time 8s; Electroplating Pt metallic catalyst technological parameter is: and electroplate liquid composition (1% chloroplatinic acid: 0.0025% hydrochloric acid: 0.01% lead acetate), operating voltage 5V, working current density 300mA/cm
2, operating time 10s.
(5) will contain 2 * 8cm
2the sheet glass of groove is placed on above-mentioned substrate, utilizes binding agent by silicon chip and sheet glass tight bond, has completed cell package.
The miniature battery performance without membrane cell of the carbon nanotubes stereo electrod that the present invention prepares: take formic acid as fuel, hydrogen peroxide be oxidant, the Pt/Au loading on carbon nanotube electrode of take is anode catalyst, the Pt loading on carbon nanotube electrode is cathod catalyst, and maximum power density reaches 6.35mW/cm
2, fuel availability is 80%.
Carbon nanotubes stereo electrod miniature without a membrane cell, prepares by the following method, specifically comprises the steps:
(1) at substrate, prepare metal electrode lead-in wire: the method for preparing metal electrode lead-in wire with embodiment 1 is identical.
(2) on Cr/Au metal lead wire, print the catalyst pulp for catalyzed carbon nanotube growth:
1.1 according to the status requirement (see figure 2) of carbon nano-tube stereo electrod and water conservancy diversion web plate, take PDMS(dimethyl silicone polymer) be material, preparation PDMS seal;
1.2 utilize PDMS Transfer seal that the catalyst pulp of nano nickel particles and polyacrylamide composition is printed on Cr/Au metal lead wire, and the effect of this catalyst pulp is the growth of catalyzed carbon nanotube.
(3) on the above-mentioned Cr/Au metal lead wire that is printed with catalyst pulp, utilize radio frequency plasma chemical vapour deposition technique direct growth to go out carbon nano-tube stereo electrod and water conservancy diversion web plate, concrete preparation technology is: chamber pressure 300Pa, radio-frequency power 450W, methane flow 2sccm, hydrogen flowing quantity 60sccm, time 60min.Carbon nano-tube stereo electrod and water conservancy diversion web plate region are 3 * 8cm
2, the high 70 μ m of stereoscopic electric, each carbon nano-tube stereo electrod electrode area is 10000 μ m
2, spacing between electrodes is 100 μ m; Each water conservancy diversion web plate width 50 μ m, high 70 μ m, between web plate, spacing is 100 μ m.
(4) substrate of carbon nanotubes and water conservancy diversion web plate is soaked in the solution that contains chloroplatinic acid and silver nitrate, soak 18 hours, taking-up utilizes hydrogen plasma reduction after drying, acquisition loads on the Pt/Ag alloy catalyst in carbon nano-tube, described reducing condition is microwave power 100W, chamber pressure 1kPa, hydrogen flow rate 10sccm.
(5) will contain 3 * 8cm
2the sheet glass of groove is placed on above-mentioned substrate, utilizes binding agent by two sheet glass tight bond, has completed cell package.
The miniature battery performance without membrane cell of the carbon nanotubes stereo electrod that the present invention prepares: take methyl alcohol as fuel, hydrogen peroxide be oxidant, the Pt/Ag loading on carbon nanotube electrode of take is anode catalyst, the Pt/Ag loading on carbon nanotube electrode is cathod catalyst, and maximum power density reaches 5.36mW/cm
2, fuel availability is 78%.
Obviously, above-described embodiment is to be only the example that clearly explanation is done, and the not restriction to execution mode.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all execution modes.And the apparent variation of therefore amplifying or change are still within the protection range in the invention.
Claims (10)
1. a carbon nanotubes stereo electrod is miniature without membrane cell, it is characterized in that, on the described miniature baseplate material surface without membrane cell, there is metal electrode lead-in wire, the upper located growth of described metal electrode lead-in wire has a plurality of carbon nano-tube stereo electrods and a plurality of carbon nano-tube water conservancy diversion web plate, on described carbon nano-tube stereo electrod, load has catalyst, and described baseplate material is with miniature without membrane cell containing obtaining after the encapsulation of fluted cover plate bonding.
2. miniature without membrane cell according to claim 1, it is characterized in that, described baseplate material is silicon chip or sheet glass.
3. miniature without membrane cell according to claim 1, it is characterized in that, described metal electrode lead-in wire is chromium-Jin double-level-metal contact conductor.
4. miniature without membrane cell according to claim 1, it is characterized in that, described carbon nano-tube stereo electrod is to consist of numerous carbon nano-tube fasciculations, the area of each carbon nano-tube stereo electrod is 20～10000 μ m
2height is 20～200 μ m, spacing between carbon nano-tube stereo electrod and carbon nano-tube stereo electrod is 20～100 μ m, described carbon nano-tube water conservancy diversion web plate is comprised of carbon nano-tube, be linear, the width of each water conservancy diversion web plate is 10～50 μ m, and height is 20～200 μ m, and the spacing between water conservancy diversion web plate and water conservancy diversion web plate is 20～100 μ m.
5. miniature without membrane cell according to claim 1, it is characterized in that, described catalyst is metallic catalyst or the alloy catalyst of platinum, palladium, copper, gold, silver.
6. miniature without membrane cell according to claim 1, it is characterized in that, the degree of depth of described groove is consistent with the height of carbon nanotube electrode and carbon nano-tube water conservancy diversion web plate, and the length and width size of described groove is consistent with the upper carbon nanotube electrode of located growth of metal electrode lead-in wire and the area size of carbon nano-tube water conservancy diversion web plate.
7. as claim 1～6(any one) as described in the miniature preparation method without membrane cell of carbon nanotubes stereo electrod, it is characterized in that comprising the steps:
(1) on baseplate material, prepare metal electrode lead-in wire;
(2) adopt micro-contact-printing, printing is for the catalyst pulp of catalyzed carbon nanotube growth on above-mentioned metal electrode lead-in wire to utilize PDMS Transfer seal, and the printing position of described catalyst pulp on metal electrode lead-in wire be the determining positions on metal electrode lead-in wire by carbon nano-tube stereo electrod and carbon nano-tube water conservancy diversion web plate;
(3) on the above-mentioned metal electrode that is printed with catalyst pulp goes between, adopt chemical vapour deposition technique located growth carbon nano-tube stereo electrod and carbon nano-tube water conservancy diversion web plate;
(4) on above-mentioned carbon nano-tube stereo electrod load for the catalyst of oxygenated fuel and oxygen reduction agent;
(5) by after the cover plate containing groove and the encapsulation of baseplate material bonding, obtain the miniature without membrane cell of carbon nanotubes stereo electrod.
8. preparation method according to claim 7, is characterized in that, described catalyst pulp is iron, cobalt, nickel nano-metal particle or iron content, cobalt, the slaine of nickel and the mixture of organic adhesive, and described organic adhesive is polyethylene glycol or polyacrylamide.
9. preparation method according to claim 7, it is characterized in that, described chemical vapour deposition technique is microwave plasma CVD method, or radio frequency plasma chemical vapour deposition technique, the operating condition of described microwave plasma CVD method is: chamber pressure 0.2～8kPa, carbon source flow 1～5sccm, hydrogen flowing quantity 20～100sccm, time 10～80min, microwave power is 300～800W, the operating condition of described radio frequency plasma chemical vapour deposition technique is: chamber pressure 0.2～8kPa, carbon source flow 1～5sccm, hydrogen flowing quantity 20～100sccm, time 10～80min, radio-frequency power is 200～450W, described carbon source is methane, acetone or ethanol.
10. preparation method according to claim 7, it is characterized in that, the method of the described supported catalyst of step (4) is: growth is had the baseplate material of carbon nano-tube and water conservancy diversion web plate to be soaked in to contain in the salting liquid of platinum, palladium, copper, gold and/or silver, soak 5～24 hours, taking-up utilizes hydrogen plasma, hydrogen or sodium borohydride reduction after drying, obtain and load on metallic catalyst or the alloy catalyst in carbon nano-tube; Or take metal electrode lead-in wire as negative pole, and baseplate material is placed in to electroplating bath, the salting liquid that contains platinum, palladium, copper, gold and/or silver of take is electroplate liquid, obtains metallic catalyst or the alloy catalyst loading in carbon nano-tube by plating.
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| CN201310631030.8A CN103682372B (en) | 2013-11-29 | 2013-11-29 | A kind of carbon nanotubes stereo electrod miniature without membrane cell and preparation method thereof |
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| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| US11633785B2 (en) | 2019-04-30 | 2023-04-25 | 6K Inc. | Mechanically alloyed powder feedstock |
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| US11963287B2 (en) | 2020-09-24 | 2024-04-16 | 6K Inc. | Systems, devices, and methods for starting plasma |
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| US11839919B2 (en) | 2015-12-16 | 2023-12-12 | 6K Inc. | Spheroidal dehydrogenated metals and metal alloy particles |
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| US11633785B2 (en) | 2019-04-30 | 2023-04-25 | 6K Inc. | Mechanically alloyed powder feedstock |
| US11717886B2 (en) | 2019-11-18 | 2023-08-08 | 6K Inc. | Unique feedstocks for spherical powders and methods of manufacturing |
| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| US11855278B2 (en) | 2020-06-25 | 2023-12-26 | 6K, Inc. | Microcomposite alloy structure |
| US11963287B2 (en) | 2020-09-24 | 2024-04-16 | 6K Inc. | Systems, devices, and methods for starting plasma |
| US11919071B2 (en) | 2020-10-30 | 2024-03-05 | 6K Inc. | Systems and methods for synthesis of spheroidized metal powders |
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