CN103682383B - Micro membrane-free fuel cell with three-dimensional porous carbon electrode and preparation method thereof - Google Patents
Micro membrane-free fuel cell with three-dimensional porous carbon electrode and preparation method thereof Download PDFInfo
- Publication number
- CN103682383B CN103682383B CN201310632092.0A CN201310632092A CN103682383B CN 103682383 B CN103682383 B CN 103682383B CN 201310632092 A CN201310632092 A CN 201310632092A CN 103682383 B CN103682383 B CN 103682383B
- Authority
- CN
- China
- Prior art keywords
- metal electrode
- carbon
- miniature
- cnt
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- 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
- H01M4/8605—Porous electrodes
-
- 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
-
- 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
- H01M4/8853—Electrodeposition
-
- 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
-
- 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 a three-dimensional porous carbon electrode and a preparation method thereof. The surface of a metal electrode lead is loaded with a carbon nanotube with a certain-thickness or carbon fiber to form the three-dimensional porous carbon electrode, and then is bonded and packaged by a cover slip to prepare the micro membrane-free fuel cell. The fuel and oxidant of the fuel cell respectively penetrate the three-dimensional porous carbon electrode loaded with a catalyst in a penetrative mode to conduct oxidation and reduction reaction, and a reactant (fuel and oxidant) liquid flow has high-efficient diffusion/convection substance transmission characteristics during penetrating the three-dimensional electrode. Reactants near an electrode consumption boundary layer can obtain sustained and effective supplement, so that the reactant concentration at the electrode can maintain a certain value. Meanwhile, as the carbon nanotube or the carbon fiber are loose and porous and have large specific surface area and more reactivity areas, the micro fuel cell has high fuel availability and a high power density.
Description
Technical field
The invention belongs to field of fuel cell technology, more particularly to a kind of miniature nothing containing 3 D stereo porous carbon electrodes
Membrane cell and preparation method thereof.
Background technology
With the development of science and technology, mobile electronic device is constantly miniaturized, for micro high efficiency power supply requirement increasingly
Greatly.Micro fuel cell has high-energy conversion efficiency, high-specific-power, high power capacity, small volume and advantages of environment protection, can
The growing energy demand of mobile electronic device is met to a certain extent, it is increasingly general with all kinds of mobile electronic devices
And, the demand of micro fuel cell will be projected more, be a kind of potential technology.
Miniature is a kind of new micro fuel cell without the need for PEM without membrane cell, and it makes full use of miniflow
The co-layer stream attribute that body viscosity is relatively strong and occurs, i.e. two strands of liquid streams of oxidant and fuel are interacted when passing through each other in micro- raceway groove
There is the characteristic of less mixing in contact surface.PEM is played a part of in fluid-flow contact face, thus can regard fluid-flow contact face as
Virtual PEM, it is miniature also to realize the selective penetrated property of proton so as to keep without the need for PEM without membrane cell
Internal circuit is unimpeded when battery operated.
In a fuel cell, all of redox reaction is all based on what planar electrode surface was carried out.It is existing miniature
Electrode without membrane cell is generally that strip is plane, is distributed in the both sides of microchannel, and fuel and oxidant exist respectively
Anode and cathode surface flow through and redox reaction occur.It is current it is miniature without membrane cell be using metal material as
Electrode, brushes or deposited catalyst on electrode, or brushing is loaded with carrier material of catalyst etc. on electrode.But by this
Anodizing reduction reaction prepared by a little methods is confined to two dimensional surface, reactivity region face limitation, fuel availability and work(
Rate density is low.
The content of the invention
Fuel-cell fuel utilization rate is low and power density is low in order to solve the problems, such as prior art, the invention provides
It is a kind of containing the miniature without membrane cell and preparation method thereof of 3 D stereo porous carbon electrodes.
It is a kind of miniature without membrane cell containing 3 D stereo porous carbon electrodes, the miniature substrate without membrane cell
There is metal electrode lead on material surface, CNT or carbon fiber, the carbon nanometer are loaded with the metal electrode lead
Catalyst is loaded with pipe or carbon fiber, the metal electrode lead is constituted with the CNT or carbon fiber that are loaded with catalyst
3 D stereo porous carbon electrodes, the miniature fuel without membrane cell and oxidant are respectively through negative in the form of permeating
There is redox reaction in the 3 D stereo porous carbon electrodes for being loaded with catalyst, obtain after the baseplate material and cover plate bonding encapsulation
To miniature without membrane cell.
In such scheme, the baseplate material is silicon chip or sheet glass.
In such scheme, the metal electrode lead is chromium metal film electrode lead.
In such scheme, the thickness of the porous CNT or carbon fiber is 0.1～1mm.
In such scheme, the catalyst is platinum, palladium, copper, the metallic catalyst of gold, silver or alloy catalyst.
It is a kind of to prepare the above-mentioned miniature method without membrane cell containing 3 D stereo porous carbon electrodes, including following step
Suddenly：（1）Metal electrode lead is prepared on baseplate material；
（2）CNT or carbon nano-fiber are loaded on metal electrode lead；
（3）The supported catalyst on CNT or carbon nano-fiber；
（4）To obtain miniature without membrane cell after aforesaid substrate material and cover plate bonding encapsulation.
In such scheme, the preparation method of the metal electrode lead is：Prepare metal film on baseplate material first；So
Coat one layer of photoresist in the metallic film surface afterwards；Again photoetching and development treatment are carried out to the photoresist, make the metal
Electrode pattern needed for remaining photoresist is presented on film, subsequently puts it in etching liquid and performs etching, and obtains required electricity
Pole shape；The photoresist after finally carbonization is etched, the photoresist after the etching is put in high temperature furnace carries out heat treatment.
Aforesaid substrate material is silicon chip or glass, and above-mentioned metal film is chromium-gold double-layer metal film, and above-mentioned etching liquid is chromium
Etching liquid, the above-mentioned method for preparing metal film is sputtering method, magnetron sputtering method or thermal evaporation plating method；Specifically, the magnetic control splashes
The method of penetrating prepares the technological parameter of the metal film：Chamber pressure be 0.5～0.6Pa, sputtering power be 80～100W, argon stream
Speed is 10～12cm2/ min, sputtering time is 2～3min；One layer of light is coated in the metallic film surface using spin coating method
Photoresist, the technological parameter of the spin coating method is：Rotating speed is 700～800rpm, and the time is 6～9s, then Jing rotating speeds are 3500rpm,
Time is 20～30s；The process of thermal treatment parameter is：Heated up with the speed of 1～2 DEG C/min, in 150 DEG C of temperature conditionss
Under, 0.5h is incubated, then 350～380 DEG C, after insulation 0.5h are warming up to the speed of 5 DEG C/min, furnace cooling.
In such scheme, the carrying method of the porous CNT or carbon nano-fiber is：Direct precipitation method, electrophoresis sink
Area method or direct growth method.
The step of above-mentioned direct precipitation method is：By CNT or carbon fiber ultrasonic disperse in acetone soln, will mix
Drop is added to the metal lead wire surface precipitation, then 50 DEG C～80 DEG C of Jing, 15～30min drying.
The step of above-mentioned electrophoretic deposition is：Take carbon nano-tube aqueous solutions or carbon fiber that concentration is 0.5～2g/l water-soluble
Liquid, deposition voltage is 1～2v, and sedimentation time is 5～10h.
Above-mentioned direct growth method loads the processing step of the CNT：It is first heavy in metal lead wire surface electrophoresis
Product Ni, deposition voltage is 3～5v, and sedimentation time is 15～30s, and then using microwave plasma device, microwave power is 250
～350W, growth time is 30～60min, and operating air pressure is 2.5～3.5kpa, and hydrogen flowing quantity is 50～55cm3/ min, methane
Flow is 3.3～3.5cm3/min。
Above-mentioned direct growth method loads the processing step of the carbon fiber：First in metal lead wire surface electrophoretic deposition
Ni, deposition voltage be 1～3v, sedimentation time be 15～30s, then using microwave plasma device, microwave power be 200～
300W, growth time is 30～60min, and operating air pressure is 4～5kpa, and hydrogen flowing quantity is 50～55cm3/ min, methane flow is
3.3～3.5cm3/min。
In such scheme, the catalyst is general platinum, palladium, copper, gold, silver metallic catalyst or alloy catalyst.
In such scheme, the method for the supported catalyst is：The substrate of CNT or carbon nano-fiber will be loaded with
Material is soaked in the saline solution containing platinum, palladium, copper, gold, and/or silver, is soaked 5～24 hours, and taking-up utilizes hydrogen etc. after drying
Gas ions, hydrogen or sodium borohydride reduction, acquisition loads metallic catalyst on the carbon nanotubes or alloy catalyst；Or with gold
Category contact conductor is negative pole, baseplate material is placed in electroplating bath, with the saline solution containing platinum, palladium, copper, gold, and/or silver as electricity
Plating solution, load metallic catalyst on the carbon nanotubes or alloy catalyst are obtained by electroplating.
Beneficial effects of the present invention：The present invention's is miniature without membrane cell, using the 3 D stereo for being loaded with catalyst
CNT or carbon fiber are stood respectively in the form of permeating as electrode, fuel and oxidant through the three-dimensional for being loaded with catalyst
There is redox reaction, reactant in body carbon electrode（Fuel and oxidant）Liquid stream has efficient expansion when passing through stereo electrod
/ convection current mass transfer characteristic is dissipated, therefore the reactant near consumption of electrode boundary region can obtain the supplement of continuous and effective so that
Reactant concentration can maintain certain value at electrode；Simultaneously because CNT or carbon fiber are loose porous and with big specific surface
Product, reactivity region is more, therefore micro fuel cell of the present invention has high fuel availability and power density.
Description of the drawings
Fig. 1 is micro fuel cell structures schematic diagram of the present invention, wherein 1 is metal electrode lead, 2 is 3 D stereo porous
CNT or carbon fiber, 3 is oxidant, and 4 is fuel.
Specific embodiment
For a better understanding of the present invention, present disclosure is further elucidated with reference to embodiment, but the present invention
Content is not limited solely to example below.
Embodiment 1
It is a kind of containing the miniature without membrane cell of 3 D stereo porous carbon electrodes, be prepared via a method which to obtain, specifically
Comprise the steps：
（1）Metal electrode lead is prepared in substrate：
1.1 using magnetron sputtering method in the sheet glass for cleaning up（Substrate）One layer of chromium metal film of upper preparation, the chromium metal
Film is used as the lead of carbon electrode.The technological parameter of magnetron sputtering method is：Chamber pressure 0.6Pa, sputtering power 100W, argon flow velocity
12cm2/ min, sputtering time 2min；
1.2 coat one layer of photoresist using sol evenning machine on chromium metal film, and the technological parameter of spin coating is：Low speed 800rpm is left
The right side, time 6s, high speed 3500rpm, time 30s；
1.3 pairs of photoresists carry out the process such as photoetching, development, and graphical photoresist makes photoresist remaining on chromium metal film
Electrode pattern needed for presenting, then etching in chromium etching liquid is put it into, the crome metal for manifesting is removed, obtain required electrode
Shape；
1.4 are put into the sheet glass after above-mentioned operation is processed in high temperature furnace, and be carbonized photoresist, and technological parameter is：With 1
DEG C/speed of min heats up, and under 150 DEG C of temperature conditionss, is incubated 0.5h, is then warming up to 380 DEG C with the speed of 5 DEG C/min,
After insulation 0.5h, furnace cooling obtains Cr/Au metal electrode leads.
（2）CNT is loaded on metal electrode lead：Deposited in metal electrode wire surface using direct precipitation method
CNT, CNT described in 0.2g is added in 15ml acetone solns, ultrasonic mixing 15min, magnetic agitation 15min, will
Mixed liquor is added drop-wise to the metal electrode wire surface precipitation, then through 80 DEG C, 15min drying, acquisition is supported on metal electrode
CNT on lead, described CNT thickness 0.5mm or so.
（3）Supported catalyst on the carbon nanotubes：The substrate for being loaded with metal electrode lead and CNT is soaked in
In solution containing chloroplatinic acid and copper nitrate, soak 18 hours, take out after room temperature is dried and reduced using hydrogen plasma, born
The CNT solid anode and cathode electrode of Pt/Cu alloy catalysts are loaded with, the hydrogen plasma reducing condition is microwave
Power 100W, chamber pressure 1kPa, hydrogen flow rate 10sccm.
（4）To obtain miniature without membrane cell after substrate and cover plate bonding encapsulation.
The miniature battery performance without membrane cell containing 3 D stereo porous carbon electrodes that the present invention is prepared：With V2+
For fuel, VO2 +For oxidant, maximum power density reaches 116mW/cm2, fuel availability is 90%, it is seen that prepared by the present embodiment
Fuel cell there is higher electrical power density and fuel availability.
Embodiment 2
It is a kind of containing the miniature without membrane cell of 3 D stereo porous carbon electrodes, be prepared via a method which to obtain, specifically
Comprise the steps：
（1）Metal electrode lead is prepared in substrate：
1.1 using magnetron sputtering method in the silicon chip for cleaning up（Substrate）One layer of chromium metal film of upper preparation, magnetron sputtering method
Technological parameter be：Chamber pressure 0.5Pa, sputtering power 80W, argon flow velocity 10cm2/ min, sputtering time 3min；
1.2 coat one layer of photoresist using sol evenning machine on chromium metal film, and the technological parameter of spin coating is：Low speed 700rpm is left
The right side, time 9s, high speed 3500rpm, time 20s；
1.3 pairs of photoresists carry out the process such as photoetching, development, and graphical photoresist makes photoresist remaining on chromium metal film
Electrode pattern needed for presenting, then etching in chromium etching liquid is put it into, the crome metal for manifesting is removed, obtain required electrode
Shape；
1.4 are put into the silicon chip after above-mentioned operation is processed in high temperature furnace, and be carbonized photoresist, and technological parameter is：With 2
DEG C/speed of min heats up, and under 150 DEG C of temperature conditionss, is incubated 0.5h, is then warming up to 350 DEG C with the speed of 5 DEG C/min,
After insulation 0.5h, furnace cooling obtains Cr/Au metal electrode leads.
（2）Carbon nano-fiber is loaded on metal electrode lead：It is heavy in metal electrode wire surface using direct precipitation method
Carbon distribution fiber, carbon fiber described in 0.5g is added in 25ml acetone solns, ultrasonic mixing 15min, magnetic agitation 15min, will be mixed
Close drop and be added to the metallic film surface precipitation, then through 50 DEG C, 30min drying, acquisition is supported on metal electrode lead
CNT, described CNT thickness 1mm or so.
（3）The supported catalyst on carbon nano-fiber：Take 2ml0.0056mol/L's（NH4）2PdCl6And 2ml
The H of 0.0039mol/L2PtCl6·6H2Carbon fibre anodes and negative electrode of the O respectively to obtaining carries out incipient impregnation, dip time
For 24 hours, then reduced using hydrogen plasma, microwave power is 100w, and the recovery time is 30min, is loaded with respectively
The carbon fiber solid anode electrode of Pd catalyst and the carbon fiber solid cathode electrode for being loaded with Pt catalyst；
（4）To obtain miniature without membrane cell after substrate and cover plate bonding encapsulation.
The miniature battery performance without membrane cell containing 3 D stereo porous carbon electrodes that the present invention is prepared：With
HCOOH is fuel, H2O2For oxidant, maximum power density reaches 78mW/cm2, fuel availability is 90%, it is seen that the present embodiment
The fuel cell of preparation has higher cell power density and fuel availability.
Embodiment 3
It is a kind of containing the miniature without membrane cell of 3 D stereo porous carbon electrodes, be prepared via a method which to obtain, specifically
Comprise the steps：
（1）Metal electrode lead is prepared in substrate：With embodiment 1；
（2）CNT is loaded on metal electrode lead：Deposited in metal electrode wire surface using electrophoretic deposition
CNT, 2g CNTs are added in the water of 1L, and compound concentration is the carbon nano-tube aqueous solutions of 2g/l, applies the electricity of 1V
Pressure, sedimentation time 10h, acquisition is supported on the CNT on metal electrode lead, described CNT thickness 0.5mm or so；
（3）Supported catalyst on the carbon nanotubes：The substrate for being loaded with metal electrode lead and CNT is soaked in
In solution containing chloroplatinic acid and silver nitrate, soak 18 hours, take out after room temperature is dried and reduced using hydrogen plasma, born
It is loaded with the CNT solid anode and cathode electrode of Pt/Ag alloy catalysts, the reducing condition is microwave power 100W, chamber
Body pressure 1kPa, hydrogen flow rate 10sccm.
（4）To obtain miniature without membrane cell after substrate and cover plate bonding encapsulation.
The miniature battery performance without membrane cell containing 3 D stereo porous carbon electrodes that the present invention is prepared：With V2+
For fuel, VO2 +For oxidant, maximum power density reaches 112mW/cm2, fuel availability is 85%, it is seen that prepared by the present embodiment
Fuel cell have higher cell power density and fuel availability.
Embodiment 4
It is a kind of containing the miniature without membrane cell of 3 D stereo porous carbon electrodes, be prepared via a method which to obtain, specifically
Comprise the steps：
（1）Metal electrode lead is prepared in substrate：With embodiment 1；
（2）Carbon nano-fiber is loaded on metal electrode lead：It is heavy in metal electrode wire surface using electrophoretic deposition
Carbon distribution fiber, 2g carbon nano-fibers are added in the water of 1L, and compound concentration is the carbon fiber water solution of 2g/l, applies the electricity of 2V
Pressure, sedimentation time 5h, acquisition is supported on the carbon fiber on metal electrode lead, and the thickness of the carbon fiber is 0.5mm；
（3）The supported catalyst on carbon nano-fiber：Take 2ml0.0056mol/L's（NH4）2PdCl6And 2ml
The AuCl of 0.0049mol/L3.HCl.4H2Carbon fibre anodes and negative electrode of the O respectively to obtaining carries out incipient impregnation, dip time
For 24 hours, then reduced using hydrogen plasma, microwave power is 100w, and the recovery time is 30min, is loaded with respectively
The carbon fiber solid anode electrode of Pd catalyst and the carbon fiber solid cathode electrode for being loaded with Au catalyst；
（4）To obtain miniature without membrane cell after substrate and cover plate bonding encapsulation.
The miniature battery performance without membrane cell containing 3 D stereo porous carbon electrodes that the present invention is prepared：With
HCOOH is fuel, NaOCl is oxidant, and maximum power density reaches 65mW/cm2, fuel availability is 85%, it is seen that this enforcement
Fuel cell prepared by example has higher cell power density and fuel availability.
Embodiment 5
It is a kind of containing the miniature without membrane cell of 3 D stereo porous carbon electrodes, be prepared via a method which to obtain, specifically
Comprise the steps：
（1）Metal electrode lead is prepared in substrate：With embodiment 2；
（2）CNT is loaded on metal electrode lead：Loaded in metal electrode wire surface using direct growth method
CNT, first in metal electrode wire surface electrophoretic deposition Ni, electroplate liquid is the nickel nitrate solution of 0.05mol/L, during deposition
Between 15s, voltage is 3v, first Jing after hydrogen plasma process 10min then using microwave plasma device, then carries out carbon
The growth of nanotube, microwave power is 300W, and operating air pressure is 3kpa, and hydrogen flowing quantity is 55cm3/ min, methane flow is
3.3cm3/ min, growth time is 60min, is then shut off hydrogen and methane, and reduction air pressure is 0.2kpa, and holding microwave power is
300W, process time 5min, acquisition is supported on the CNT on metal electrode lead, and the thickness of the CNT is
0.1mm；
（3）Supported catalyst on the carbon nanotubes：Take the H of 2ml 0.0039mol/L2PtCl6·6H2O and 2ml
The H of 0.0039mol/L2PtCl6·6H2CNT anodes and negative electrode of the O respectively to obtaining carries out incipient impregnation, during dipping
Between be 24 hours, then using hydrogen plasma reduce, microwave power is 100w, and the recovery time is 30min, is loaded respectively
There are the CNT solid anode electrode and cathode electrode of Pt catalyst；
（4）To obtain miniature without membrane cell after substrate and cover plate bonding encapsulation.
The miniature battery performance without membrane cell containing 3 D stereo porous carbon electrodes that the present invention is prepared with
CH3OH is fuel, KMnO4For oxidant, maximum power density reaches 85mW/cm2, fuel availability is 80%, it is seen that this enforcement
Fuel cell prepared by example has higher cell power density and fuel availability.
Embodiment 6
It is a kind of containing the miniature without membrane cell of 3 D stereo porous carbon electrodes, be prepared via a method which to obtain, specifically
Comprise the steps：
（1）Metal electrode lead is prepared in substrate：With embodiment 2；
（2）Carbon nano-fiber is loaded on metal electrode lead：It is negative in metal electrode wire surface using direct growth method
Carbon fiber is carried, first in metal electrode wire surface electrophoretic deposition Ni, electroplate liquid is the nickel nitrate solution of 0.05mol/L, during deposition
Between 30s, voltage is 1v, first Jing after hydrogen plasma process 20min then using microwave plasma device, then carries out carbon
The growth of fiber, microwave power 200W, operating air pressure 5kpa, growth time 30min, hydrogen flowing quantity is 55cm3/ min, methane stream
Measure as 3.3cm3/ min, acquisition is supported on the carbon fiber on metal electrode lead, the carbon fiber thickness 1mm；
（3）The supported catalyst on porous carbon nanofiber：With embodiment 4；
（4）To obtain miniature without membrane cell after substrate and cover plate bonding encapsulation.
The present invention prepare containing the miniature without the cell performance of membrane cell of 3 D stereo porous carbon electrodes：With V2+For
Fuel, VO2 +For oxidant, maximum power density reaches 115mW/cm2, fuel availability is 90%, it is seen that manufactured in the present embodiment
Fuel cell has higher cell power density and fuel availability.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and not to the restriction of embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need to be exhaustive to all of embodiment.And therefore the obvious change amplified or change
Move within still in the protection domain of the invention.
Claims (9)
1. it is a kind of containing the miniature without membrane cell of 3 D stereo porous carbon electrodes, it is characterised in that described miniature without membrane fuel
There is metal electrode lead on the baseplate material surface of battery, on the metal electrode lead CNT or carbon fiber be loaded with,
Catalyst, the metal electrode lead and the carbon nanometer for being loaded with catalyst are loaded with the CNT or carbon fiber
Pipe or carbon fiber constitute 3 D stereo porous carbon electrodes, and the miniature fuel without membrane cell and oxidant are respectively oozing
Saturating form penetrates flow through the 3 D stereo porous carbon electrodes for being loaded with catalyst generation redox reaction, the substrate in opposite directions
Obtain miniature without membrane cell after material and cover plate bonding encapsulation；The CNT being supported on metal electrode or carbon are fine
The thickness of dimension is 0.1 ~ 1mm.
2. it is according to claim 1 miniature without membrane cell, it is characterised in that the baseplate material is silicon chip or glass
Piece.
3. it is according to claim 1 miniature without membrane cell, it is characterised in that the metal electrode lead is chromium metal
Membrane electrode lead.
4. according to claim 1 miniature without membrane cell, it is characterised in that the catalyst be metallic catalyst or
Alloy catalyst, the metallic catalyst is platinum, palladium, copper, gold or silver, and the alloy catalyst is in platinum, palladium, copper, gold and silver
Several metals formed alloy catalyst.
5. a kind of miniature preparation without membrane cell containing 3 D stereo porous carbon electrodes as described in any one of claim 1 ~ 4
Method, it is characterised in that comprise the steps：
（1）Metal electrode lead is prepared on baseplate material；
（2）CNT or carbon nano-fiber are loaded on metal electrode lead；
（3）The supported catalyst on CNT or carbon nano-fiber；
（4）To obtain miniature without membrane cell after aforesaid substrate material and cover plate bonding encapsulation.
6. preparation method according to claim 5, it is characterised in that described that CNT or carbon are loaded on metal electrode
The method of nanofiber is：Direct precipitation method, electrophoretic deposition or direct growth method.
7. preparation method according to claim 6, it is characterised in that be the step of the direct precipitation method：By carbon nanometer
Mixed liquor is added drop-wise to the metal electrode wire surface precipitation, then Jing 50 by pipe or carbon fiber ultrasonic disperse in acetone soln
DEG C ~ 80 DEG C, 15 ~ 30min drying.
8. preparation method according to claim 6, it is characterised in that be the step of the electrophoretic deposition：Taking concentration is
The carbon nano-tube aqueous solutions or carbon fiber water solution of 0.5 ~ 2g/l, deposition voltage is 1 ~ 2v, and sedimentation time is 5 ~ 10 h.
9. preparation method according to claim 6, it is characterised in that the direct growth method loads the CNT
Processing step is：First in the metal electrode wire surface electrophoretic deposition Ni, deposition voltage is 3 ~ 5v, sedimentation time is 15 ~
30s, then using microwave plasma device direct growth CNT, microwave power be 250 ~ 350W, growth time be 30 ~
60min, operating air pressure is 2.5 ~ 3.5kpa, and hydrogen flowing quantity is 50 ~ 55 cm3/ min, methane flow is 3.3 ~ 3.5 cm3/min；
The direct growth method loads the processing step of the carbon fiber：First in the metal electrode wire surface electrophoretic deposition Ni,
Deposition voltage is 1 ~ 3v, and sedimentation time is 15 ~ 30s, then using microwave plasma device direct growth carbon fiber, microwave work(
Rate is 200 ~ 300W, and growth time is 30 ~ 60min, and operating air pressure is 4 ~ 5kpa, and hydrogen flowing quantity is 50 ~ 55 cm3/ min, methane
Flow is 3.3 ~ 3.5 cm3/min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310632092.0A CN103682383B (en) | 2013-11-29 | 2013-11-29 | Micro membrane-free fuel cell with three-dimensional porous carbon electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310632092.0A CN103682383B (en) | 2013-11-29 | 2013-11-29 | Micro membrane-free fuel cell with three-dimensional porous carbon electrode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103682383A CN103682383A (en) | 2014-03-26 |
| CN103682383B true CN103682383B (en) | 2017-05-03 |
Family
ID=50319207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310632092.0A Expired - Fee Related CN103682383B (en) | 2013-11-29 | 2013-11-29 | Micro membrane-free fuel cell with three-dimensional porous carbon electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103682383B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985881B (en) * | 2014-04-29 | 2016-04-13 | 华南理工大学 | The preparation method of a kind of three-dimensional poroid carbon foam stand electrode and application |
| CA3009630C (en) | 2015-12-16 | 2023-08-01 | Amastan Technologies Llc | Spheroidal dehydrogenated metals and metal alloy particles |
| CN106129816B (en) * | 2016-08-16 | 2017-08-11 | 华东师范大学 | A kind of method and device for improving ion wind wind speed |
| CN109607698B (en) * | 2019-01-07 | 2021-08-10 | 大连理工大学 | Method for preparing massive flat porous formed carbon electrode |
| AU2020264446A1 (en) | 2019-04-30 | 2021-11-18 | 6K Inc. | Mechanically alloyed powder feedstock |
| WO2021118762A1 (en) | 2019-11-18 | 2021-06-17 | 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 |
| EP4173060A1 (en) | 2020-06-25 | 2023-05-03 | 6K Inc. | Microcomposite alloy structure |
| AU2021349358A1 (en) | 2020-09-24 | 2023-02-09 | 6K Inc. | Systems, devices, and methods for starting plasma |
| AU2021371051A1 (en) | 2020-10-30 | 2023-03-30 | 6K Inc. | Systems and methods for synthesis of spheroidized metal powders |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101515648A (en) * | 2009-03-19 | 2009-08-26 | 同济大学 | Novel membrane electrode component available for fuel cell, preparation method and application thereof |
| CN102916200A (en) * | 2012-10-31 | 2013-02-06 | 武汉工程大学 | Method for preparing electrode of miniature film-free fuel cell |
| CN103401000A (en) * | 2013-08-14 | 2013-11-20 | 西南石油大学 | Catalyst for proton exchange membrane fuel battery, preparation method for catalyst and proton exchange membrane fuel battery |
-
2013
- 2013-11-29 CN CN201310632092.0A patent/CN103682383B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101515648A (en) * | 2009-03-19 | 2009-08-26 | 同济大学 | Novel membrane electrode component available for fuel cell, preparation method and application thereof |
| CN102916200A (en) * | 2012-10-31 | 2013-02-06 | 武汉工程大学 | Method for preparing electrode of miniature film-free fuel cell |
| CN103401000A (en) * | 2013-08-14 | 2013-11-20 | 西南石油大学 | Catalyst for proton exchange membrane fuel battery, preparation method for catalyst and proton exchange membrane fuel battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103682383A (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103682383B (en) | Micro membrane-free fuel cell with three-dimensional porous carbon electrode and preparation method thereof | |
| CN103682372B (en) | A kind of carbon nanotubes stereo electrod miniature without membrane cell and preparation method thereof | |
| CN103280583B (en) | Method for preparing catalytic layer structure of proton exchange membrane fuel cell | |
| CN105633420B (en) | A kind of nano-porous gold is used for the preparation method of fuel cell thin layer electrode | |
| CN102916199B (en) | Preparation method of fuel cell membrane electrode | |
| CN105688935B (en) | A kind of preparation method of Pt/Cu Ni catalyst and its method and the application of catalytic oxidation of alcohol | |
| JP6025230B2 (en) | Inverse opal structure metal catalyst electrode for fuel cell and manufacturing method thereof | |
| CN102916198B (en) | Fuel cell membrane electrode | |
| TWI446620B (en) | Biofuel cell | |
| CN109037715A (en) | A kind of ultralow platinum content catalyst and preparation method for fuel cell | |
| CN106816614B (en) | The fuel cell preparation of fine and close platinum monoatomic layer catalysis and electrode and application | |
| CN108722453A (en) | A kind of phosphating sludge/carbon composite nano-material for alkaline electrocatalytic hydrogen evolution | |
| CN106252670A (en) | Use the electrode added with crystal seed by the nucleocapsid catalyst volume to volume manufacture to high performance fuel cell electrode | |
| CN105047963A (en) | Novel fuel cell manufacturing method based on graphene thermoelectric management layer | |
| CN104701549B (en) | A carbon-free membrane electrode assembly | |
| CN101997123B (en) | Nano porous alloy fuel battery catalyst and preparation method thereof | |
| CN109546166B (en) | Pt/metallic carbide/carbon nano material catalyst and preparation method thereof | |
| CN112310416B (en) | Method for preparing ordered fuel cell membrane electrode | |
| CN106159286A (en) | A kind of modified electrode being applied to zinc-bromine flow battery and preparation method thereof | |
| CN103367768A (en) | Method for preparing double-catalyst-layer structure of proton exchange membrane fuel cell | |
| CN103326032B (en) | Method for preparing platinum gradient-distribution catalyst layer structure of proton exchange membrane fuel cell | |
| CN102760899B (en) | Single electrode and ordered membrane electrode based on active metal and conductive polymeric coaxial nanowire and preparation method thereof | |
| JP2007213988A (en) | Electrode catalyst layer for polymer electrolyte fuel cell, its manufacturing method, and polymer electrolyte fuel cell | |
| TWI446617B (en) | Fuel cell | |
| CN103825032B (en) | A kind of infusion process preparation has the method for the Solid Oxide Fuel Cell of double-hole structure anode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170503 Termination date: 20191129 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |