CN108232204A - A kind of silicon base ordered polarizing electrode and its preparation method and application - Google Patents
A kind of silicon base ordered polarizing electrode and its preparation method and application Download PDFInfo
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
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- 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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention provides a kind of silicon base ordered polarizing electrode and its preparation method and application, the silicon base ordered polarizing electrode, using gas diffusion layers or dielectric film as substrate, the electrode is microcosmic to be above attached with for substrate surface with silicon-based nano linear array structure arranged in parallel, silica-based nanowire perpendicular is attached to substrate surface, and the nanowire surface grows or be attached with conductive carbon layer, metal nanoparticle layer and polyion layer successively；The nanowire length is 1 100 μm；A diameter of 0.02 4 microns；The density of the nano-wire array is every square millimeter 4 × 104‑1×108A nano wire.Compared with prior art, the present invention has many advantages, such as that structurally ordered controllable, precious metal catalyst activity height, noble metal utilisation height, mass-transfer performance are good, highly practical.
Description
Technical field
The present invention relates to a kind of orderly composite nano materials of new multistage and its structure, specifically this material has
There is carbon-coating modification to be modified with nano platinum particle layer for a kind of ordered nano linear array, nanowire surface, and outermost layer has perfluor sulphur
Sour polyion decorative layer can be used for Proton Exchange Membrane Fuel Cells, direct liquid fuel battery, metal-air battery and super
In the electrodes such as capacitor, electrochemical sensor.
The invention further relates to the preparation methods of above-mentioned composite material.
Background technology
Have the function of the charge-conduction of ordered nano-structure with the composite material of electro-catalysis in electronics, the energy, biological medicine
The fields of grade have huge application potential.The all kinds of of carbon are typically based in electrode suitable for the conductive material of electrochemical environment to receive
Rice material, such as carbon nanotube, graphene, activated carbon etc..The distinguishing feature that this kind of material has typically exhibits out for it
Flexible characteristic.Order and charge, the controllability of mass transfer in the application field of fuel cell electrode etc., structure are
Electrode basic process, the basic demand for illustrating electrode electro Chemical behavior.Microfluid in electrochemical environment there is with
The completely different behavioral mechanism of macrofluid, increasingly complex changeable environmental characteristic cause deeply grinding to it with transmission structure
Study carefully and be filled with difficult and challenge.Therefore, design and prepare with theoretical close model electrode structure, and develop can effective table
The means of impressing electrode process are the key points for studying electrochemical microfluidic body mass transfer behavior essence in fuel cell.It is handed over proton
It changes for membrane cell oxygen reduction reaction cathode, electrode basic process is followed successively by oxygen molecule and passes through the biographies such as convection current, diffusion
It passs and is adsorbed in the active sites such as platinum surface, the hydrogen ion migrated by proton exchange membrane further passes through the biographies such as polyion
Defeated channel migration is electrically coupled electrochemical reaction, product under certain potentials to active site with the oxygen molecule of absorption generation matter
Water leaves active site and is discharged along duct, and the electronics of generation is conducted along conductive carrier and externally done work.Include transmission gas, liquid
Body, proton, electronics four channels, be the underlying dimension of fuel cell electrode, and be parallel to the channel in mass transfer direction then
It is a kind of ideal electrode structure.
Electrode with oldered array structure is generally considered a kind of ideal platform for studying fuel cell electrode process,
One of and be likely to become the direction of membrane electrode future development.In order to study the substance transmittance process of fuel cell, this array junctions
Structure also needs to meet following condition.First, the material of forming array needs enough electric conductivity；The pore size and hole that array is formed
Gap rate can Effective Regulation in a certain range；Array surface needs the structure with proton conduction function；Finally, array material table
Face needs the catalytically-active materials of certain density.The array structure of fuel cell electrode is presently available for, is mostly based on carbon nanometer
The materials such as pipe or carbon nano-fiber.The limitation for the methods of this kind of material is due to CVD can not often realize pore size and porosity
Consistency and controllable adjustment, simultaneously because the rigidity of material in itself is insufficient, during electrode assembling its structure easily by
Destroy, can not implementation model electrode research function.On the other hand, currently for the real-time of fuel cell electrode structures and process
On-spot study method is still more deficient, and the parameters that gas-liquid substance transmits are difficult to on-line checking, also as current electrode process
The major obstacle of research.
The present invention is prepared by mould printing and chemical etching method with higher mechanical strength and structure controllable precise
Silicon based array structure, and pass through be vapor-deposited modified conducting carbon-coating and platinum base catalytic activity particle, structure have it is uniform, orderly,
Accurate in size model structure electrode.
Invention content
The present invention prepares the control for preparing a kind of oldered array model electrode based on rigid silica-base material, this electrode
With in orderly silicon nanowire array on dielectric film direction, array surface covering electrical-conductive nanometer thin layer, thin layer table
Face uniform fold metal nanoparticle, covers polyion thin layer again thereon, can be used as fuel cell, metal-air battery, electrification
Learn the porous electrode of the devices such as sensor.
To achieve the above object, the present invention is realized using scheme in detail below：
A kind of silicon base ordered polarizing electrode, the electrode are microcosmic upper with silicon-based nano linear array structure arranged in parallel, institute
It states nanowire surface and grows or be attached with conductive carbon layer, metal nanoparticle layer and polyion layer successively；The nanowire length
It is 1-100 μm；It is 0.02-4 microns a diameter of；The density of the nano-wire array is every square millimeter 4 × 104-1×108A nanometer
Line.The vertical array structure of this electrode is conducive to effective transmission of charge (including electronics and ion) and gas-liquid substance, and extends
Electrode surface, increases electrode reaction area.
The nano wire that the silica-based nanowire is monocrystalline silicon, a kind of in polysilicon, silicon carbide, silica.
The thickness of the conductive carbon layer is 1-20nm；The carrying capacity of metal nanoparticle is 0.001-0.5mg/cm2, metal receives
The grain size of rice corpuscles is 0.5-20nm, and the carrying capacity of polyion is 0.0002-0.1mg/cm2。
Carbon material in the conductive carbon layer is graphitic carbon, one kind in agraphitic carbon, graphene, conducting polymer；Institute
Metal nanoparticle is stated as one kind in platinum, platinum palladium, platinum cobalt, platinum nickel, platinum iron, platinum silver；Polyion in the polyion layer is
Perfluorinated sulfonic acid polyion.
The preparation method of the silicon base ordered polarizing electrode, includes the following steps,
(1) it is loaded with the preparation of the silicon chip of hard template bead：The thickness of pre-treatment of learning from else's experience is 1-100 μm of silica-base material,
A diameter of 100nm to 5 μm of hard template bead homogeneous dispersion is scattered on the silicon chip, is impregnated using hard template remover
Above-mentioned silicon substrate thin slice carries out chemical attack to the hard template bead, until the small ball's diameter is contracted to original 5%-90%, must carry
There is the silica-base material of hard template bead；
(2) preparation of silicon-based nano linear array：Physical sputtering is used in the surface that hard template bead is loaded with obtained by step (1)
Method sputter one layer of metallic silver.It, then can since template bead is assembled to substrate surface by way of Electrostatic Absorption
The hard template bead on silicon chip is removed by the method for ultrasonic disperse.The base sheet of above-mentioned removing template bead is placed in chlorination
In ferrous solution, due to its effect of oxidizing corrosion to silicon base, it can be removed by the catalyst mechanism of silver by the substrate of silver covering
Layer, obtains silicon-based nano linear array；
(3) preparation of conductive decorative layer：The silicon as obtained by chemical vapor deposition or the method for electrochemical polymerization in step (2)
Base nano-wire surface deposits conductive layer, must be modified with the silicon-based nano linear array of conductive layer；The preparation of the conductive layer is conducive to
The enhancing of electronic conductance；
(4) the orderly preparation of polarizing electrode：The silica-based nanowire conductive layer table as obtained by the method for magnetron sputtering in step (3)
Face places it in polyion solution the preparation for realizing polyion layer after sputtering platinum or platinum alloy nano-particle, and washing is so dry that have
Sequence polarizing electrode.Above method preparation makes the utilization rate for being attached to ordering body structure surface, being conducive to improve catalyst of catalyst,
Reduce noble metal carrying capacity.The preparation of polyion layer is conducive to the formation of three phase boundary.
Step (1) described silica-base material is monocrystalline silicon, one kind in polysilicon, silicon carbide, silica；The silicon substrate
The pre-treatment step of material is to cut silica-base material according to a certain size, is about 1-100 μm with grinder buffing to thickness, after cleaning
With acetone soak 12 hours or more, to remove the organic impurities on surface.
Hard template bead described in step (1) be silicon ball or polystyrene sphere, the hard template bead dispersion liquid it is dense
It spends for 0.1-1%, so as to form stable colloid or suspension；The hard template corrosive agent be hydrofluoric acid, a concentration of 0.1-2M,
The chemical attack time is 10-100min, to reach required nanofiber diameter range.Step (2) is used as using high purity silver splashes
It shoots at the target material, 30W power sputtering 1min under vacuum condition；
A concentration of 0.1-2M, dip time 1-24h of step (2) described ferric chloride solution；
Step (3) described chemical vapor deposition is with methane, ethane, ethylene, acetylene, propylene, benzene, carbon monoxide, dioxy
It is carbon source to change one kind in carbon, under the conditions of 300-1000 degrees Celsius, flow velocity is 10-100mL/min, deposits 10-200min；
The electrochemical polymerization is the conducting polymer using silicon-based nano linear array obtained by step (2) as working electrode
Monomer solution is chemical polymerization solution, under opposite hydrogen electrode 0.8-1.2V potential conditions, reacts 10-200s；It is described
Conducting polymer monomer is pyrroles, one kind in aniline, thiophene, a concentration of 0.05-2M.
Step (4) described platinum alloy is platinum palladium, one kind in platinum cobalt, platinum iron, platinum nickel, platinum silver；The polyion solution is
The isopropanol or aqueous solution of perfluorinated sulfonic acid polyion, the mass concentration of the polyion solution is 0.5-10%；The metal is received
The carrying capacity of rice corpuscles is 0.001-0.5mg/cm2；The carrying capacity of the polyion is 0.0002-0.1mg/cm2.Step (4) described magnetic
Control the condition of sputtering：Environment be vacuum or Ar gas, sputtering power 5-100W, building time 1-30min.
The silicon base ordered polarizing electrode is Proton Exchange Membrane Fuel Cells or metal-air battery or electrochemical sensor
In porous electrode.
Compared with prior art, the present invention has the following advantages：
It is 1. structurally ordered controllable：The ordered nano linear array structure prepared using the method for the invention, by controlling mould
Board size all has higher structural controllability in length, diameter, array density.
2. precious metal catalyst activity is high：There is higher advantage crystalline substance using precious metal ion prepared by the method for the invention
Face exposes ratio, so as to higher catalytic activity；
3. noble metal utilisation is high：The ordered nano linear array structure prepared using the method for the invention, noble metal table
Face can be largely exposed in mass transfer channel, so as to higher utilization rate；
4. mass-transfer performance is good：The ordered nano linear array structure prepared using the method for the invention, due to its porosity
It improves, hole is orderly, and mass-transfer performance is more excellent；
It is 5. highly practical：Compared to other preparation methods, the template preparation process of this method, controllability is strong, reduces
The uncontrollable factor that other methods are brought, it is highly practical.
Description of the drawings
The preparation process and structure diagram of Fig. 1 ordered nano linear array structures of the present invention.
The stereoscan photograph of ordered nano linear array structure prepared by 1 the method for Fig. 2 embodiment of the present invention.It can see
Go out this ordered structure and show very regular array structure, nanowire length is about 2-3 μm, and nanowire diameter is about
200nm。
The transmission electron microscope photo of ordered nano linear array structure prepared by 1 the method for Fig. 3 embodiment of the present invention.It can see
Nanowire surface has grown visibly homogeneous metal nanoparticle by sputtering, and particle diameter is about 4nm or so.
Specific embodiment
Below by way of example, the present invention is described in detail, but the present invention is not limited only to following embodiment.
Embodiment 1
A. the preparation of rigid nano-wire array
Polysilicon is cut to the thin slice of 2x2cm, is about 4 μm with grinder buffing to thickness, acetone soak is used after cleaning
12h.The silicon ball of a diameter of 500nm or polystyrene sphere dispersion liquid (concentration is about 1%) are dispersed in above-mentioned thin slice.It is logical
It crosses 0.1M hydrofluoric acid and carries out chemical attack 10min, the small ball's diameter corrodes to 200nm.By physical sputtering method, by above-mentioned thin slice
Surface sputters one layer of metallic silver, and sputtering time is about 10min.The method then disperseed by ultrasonic wave removes bead template.
Above-mentioned processed thin slice is impregnated in the ferric chloride solution of 0.5M, dip time 12h passes through the catalytic machine of Ag
System removes its covering part basal layer, so as to leave unlapped nanowire array structure.The array structure of preparation such as Fig. 2 institutes
Show.
B. the preparation of conductive decorative layer
By the method for chemical vapor deposition, methane is used as carbon source, is 100mL/min conditions in 600 degrees Celsius, flow velocity
Under, above-mentioned nano-wire array surface is deposited carbon-based conductive layer by sedimentation time 10min.
C. metal particle layer and the preparation of polyion layer
By above-mentioned sample by the method for magnetron sputtering, using platinum target, sputtering power 5W, sputtering time 3min are realized
The preparation of metal nanoparticle.The results are shown in Figure 3
The sample for being supported with metallic is impregnated in the perfluorinated sulfonic acid aqueous isopropanol that mass concentration is 0.5%, turned
It prints in gas diffusion layers substrate, ordered nano linear array electrode is drying to obtain after flushing.
Embodiment 2
A. the preparation of rigid nano-wire array
Polysilicon is cut to the thin slice of 2x2cm, is about 10 μm with grinder buffing to thickness, acetone soak is used after cleaning
12h.A diameter of 1 μm of silicon ball or polystyrene sphere dispersion liquid (concentration is about 1%) are dispersed in above-mentioned thin slice.Pass through
2M hydrofluoric acid carries out chemical attack 10min, and the small ball's diameter corrodes to 800nm.By physical sputtering method, by above-mentioned sheet surface
One layer of metallic silver is sputtered, sputtering time is about 10min.The method then disperseed by ultrasonic wave removes bead template.
Above-mentioned processed thin slice is impregnated in the ferric chloride solution of 0.1M, dip time for 24 hours, passes through the catalytic machine of Ag
System removes its covering part basal layer, so as to leave unlapped nanowire array structure.
B. the preparation of conductive decorative layer
By the method for electrochemical polymerization, using pyrrole monomer aqueous solution (concentration 0.1M), 0.8V is (with respect to hydrogen standard electric
Pole) under potential condition, above-mentioned nano-wire array surface is deposited conducting polymer conductive layer by polymerization 50s.
C. metal particle layer and the preparation of polyion layer
By above-mentioned sample by the method for magnetron sputtering, using platinum target, sputtering power 10W, sputtering time 10min are real
The preparation of existing metal nanoparticle.
The sample for being supported with metallic is impregnated in the perfluorinated sulfonic acid aqueous solution that mass concentration is 10%, transfers gas
Ordered nano linear array electrode is drying to obtain in diffusion layer substrate, after flushing.
Embodiment 3
A. the preparation of rigid nano-wire array
Polysilicon is cut to the thin slice of 2x2cm, is about 10 μm with grinder buffing to thickness, acetone soak is used after cleaning
12h.The silicon ball of a diameter of 500nm or polystyrene sphere dispersion liquid (concentration is about 1%) are dispersed in above-mentioned thin slice.It is logical
Over-richness carries out chemical attack 10min for 1M hydrofluoric acid, and the small ball's diameter corrodes to 200nm.It, will be above-mentioned by physical sputtering method
Sheet surface sputters one layer of metallic silver, and sputtering time is about 10min.The method then disperseed by ultrasonic wave removes small ball mould
Plate.
Above-mentioned processed thin slice is impregnated in the ferric chloride solution of 0.1M, dip time 12h passes through the catalytic machine of Ag
System removes its covering part basal layer, so as to leave unlapped nanowire array structure.The array structure of preparation such as Fig. 2 institutes
Show.
B. the preparation of conductive decorative layer
By the method for chemical vapor deposition, methane is used as carbon source, is 100mL/min conditions in 600 degrees Celsius, flow velocity
Under, above-mentioned nano-wire array surface is deposited carbon-based conductive layer by sedimentation time 10min.
C. metal particle layer and the preparation of polyion layer
By above-mentioned sample by the method for magnetron sputtering, using platinum cobalt target, sputtering power 5W, sputtering time 3min are real
The preparation of existing metal nanoparticle.The results are shown in Figure 3
The sample for being supported with metallic is impregnated in the perfluorinated sulfonic acid aqueous isopropanol that mass concentration is 5%, transfer
Ordered nano linear array electrode is drying to obtain in gas diffusion layers substrate, after flushing.
Claims (10)
1. a kind of silicon base ordered polarizing electrode, it is characterised in that：Using gas diffusion layers or dielectric film as substrate, the electrode is microcosmic
Upper to be attached with for substrate surface with silicon-based nano linear array structure arranged in parallel, silica-based nanowire perpendicular is attached to base
Bottom surface, the nanowire surface grow or are attached with conductive carbon layer, metal nanoparticle layer and polyion layer successively；It is described to receive
Rice noodles length is 1-100 μm；It is 0.02-4 microns a diameter of；The density of the nano-wire array is every square millimeter 4 × 104-1×
108A nano wire.
2. silicon base ordered polarizing electrode as described in claim 1, it is characterised in that：The silica-based nanowire for monocrystalline silicon, polysilicon,
A kind of nano wire in silicon carbide, silica.
3. silicon base ordered polarizing electrode as described in claim 1, it is characterised in that：The thickness of the conductive carbon layer is 1-20nm；Gold
The carrying capacity for belonging to nano-particle is 0.001-0.5mg/cm2, the grain size of metal nanoparticle is 0.5-20nm, and the carrying capacity of polyion is
0.0002-0.1mg/cm2。
4. silicon base ordered polarizing electrode as described in claim 1, it is characterised in that：Carbon material in the conductive carbon layer is graphite
One kind in carbon, agraphitic carbon, graphene, conducting polymer；The metal nanoparticle is platinum, platinum palladium, platinum cobalt, platinum nickel, platinum
One kind in iron, platinum silver；Polyion in the polyion layer is perfluorinated sulfonic acid polyion.
5. a kind of preparation method of any silicon base ordered polarizing electrodes of claim 1-4, it is characterised in that：Including following step
Suddenly,
(1) it is loaded with the preparation of the silicon chip of hard template bead：The thickness of pre-treatment of learning from else's experience is 1-100 μm of silica-base material, will be straight
Diameter be 100nm to 5 μm of hard template bead homogeneous dispersion Monolayer Dispersion on the silicon chip, using hard template remover to institute
It states hard template bead and carries out chemical attack, until the small ball's diameter is contracted to original 5%-90%, the silicon of hard template bead must be loaded with
Sill；
(2) preparation of silicon-based nano linear array：The side of physical sputtering is used in the surface that hard template bead is loaded with obtained by step (1)
Method sputters one layer of metallic silver, the hard template bead on silicon chip is then removed by the method for ultrasonic disperse, and place it in chlorination
In ferrous solution, removed by the catalyst mechanism of silver by the basal layer of silver covering, obtain silicon-based nano linear array；
(3) preparation of conductive decorative layer：The silicon substrate as obtained by chemical vapor deposition or the method for electrochemical polymerization in step (2) is received
Nanowire surface deposits conductive layer, must be modified with the silicon-based nano linear array of conductive layer；
(4) the orderly preparation of polarizing electrode：The silica-based nanowire conductive layer surface as obtained by the method for magnetron sputtering in step (3) splashes
The preparation for realizing polyion layer is placed it in polyion solution after penetrating platinum or platinum alloy nano-particle, is transferred in substrate, washes
Wash dry orderly polarizing electrode.
6. the preparation method of silicon base ordered polarizing electrode as claimed in claim 5, it is characterised in that：Step (1) described silica-base material
For one kind in monocrystalline silicon, polysilicon, silicon carbide, silica；The pre-treatment step of the silica-base material is with third after cleaning
Ketone impregnates 12 hours or more.
7. the preparation method of silicon base ordered polarizing electrode as claimed in claim 5, it is characterised in that：Hard template described in step (1)
Bead is silicon ball or polystyrene sphere, and the mass concentration of the hard template bead dispersion liquid is 0.1-1%；The hard template is gone
Except agent is mass concentration 0.1-2M hydrofluoric acid, the chemical attack time is 10-100min.
8. the preparation method of silicon base ordered polarizing electrode as claimed in claim 5, it is characterised in that：Step (2) described iron chloride is molten
A concentration of 0.1-2M of liquid, dip time 1-24h；
Step (3) described chemical vapor deposition is with methane, ethane, ethylene, acetylene, propylene, benzene, carbon monoxide, carbon dioxide
In one kind for carbon source, under the conditions of 300-1000 degrees Celsius, flow velocity is 10-100mL/min, deposit 10-200min；
The electrochemical polymerization is the conducting polymer monomer using silicon-based nano linear array obtained by step (2) as working electrode
Aqueous solution is chemical polymerization solution, under opposite hydrogen electrode 0.8-1.2V potential conditions, reacts 10-200s；The conduction
Polymer monomer is pyrroles, one kind in aniline, thiophene, a concentration of 0.05-2M.
9. the preparation method of silicon base ordered polarizing electrode as claimed in claim 5, it is characterised in that：Step (4) described platinum alloy is
One kind in platinum palladium, platinum cobalt, platinum iron, platinum nickel, platinum silver；The polyion solution is the isopropanol or water-soluble of perfluorinated sulfonic acid polyion
Liquid, the mass concentration of the polyion solution is 0.5-5%；The carrying capacity of the metal nanoparticle is 0.001-0.5mg/cm2；
The carrying capacity of the polyion is 0.0002-0.1mg/cm2；The condition of step (4) described magnetron sputtering is using platinum and its alloy
One kind in target platinum palladium, platinum cobalt, platinum iron, platinum nickel, platinum silver
10. a kind of application of any silicon base ordered polarizing electrodes of claim 1-5, it is characterised in that：Silicon base orderedization
Electrode is the porous electrode in Proton Exchange Membrane Fuel Cells or metal-air battery or electrochemical sensor.
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| CN112397730A (en) * | 2020-11-08 | 2021-02-23 | 赵伟 | Preparation method of Pt/vertical orientation graphite column composite material |
| WO2023035424A1 (en) * | 2021-09-13 | 2023-03-16 | 苏州大学 | Photoelectrode and preparation method therefor, and pt-based alloy catalyst and preparation method therefor |
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