CN106711466A - Preparation method of micro-porous layer material - Google Patents
Preparation method of micro-porous layer material Download PDFInfo
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- CN106711466A CN106711466A CN201510772295.9A CN201510772295A CN106711466A CN 106711466 A CN106711466 A CN 106711466A CN 201510772295 A CN201510772295 A CN 201510772295A CN 106711466 A CN106711466 A CN 106711466A
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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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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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 field of proton exchange membrane fuel cell, and more specifically relates to a preparation method of a micro-porous layer material. According to the preparation method, inorganic oxide particles with higher electrochemical stability are used for replacing carbon powder, and construction of a high-conductivity coating layer on the surface of the inorganic oxide is carried out. The high-conductivity coating layer is capable of ensuring the original electrochemical stability of the micro-porous layer material, and providing the micro-porous layer material with better electrical conductivity. A novel cathode gas diffusion layer prepared based on the nano composite possesses corrosion stability higher than that of commercial carbon powder, and it is shown by battery performance tests that application prospect of the micro-porous layer material is promising.
Description
Technical field
The present invention relates to it is a kind of be applied to Proton Exchange Membrane Fuel Cells, with high electrochemical
The preparation method of the novel microporous layer material of stability, and in particular to a kind of to be applied with nitrating carbon
The preparation method of the oxide nano particles of layer.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is that one kind can directly convert chemical energy
It is the energy conversion device of electric energy.It is similar to internal combustion engine, as long as constantly former to its supply
Material, with regard to output electric energy that can be lasting.PEMFC has energy conversion efficiency (40- higher
60%), environmentally friendly, toggle speed is fast, long working life the advantages of, therefore undergone
To more and more extensive concern, particularly it is in automobile power, portable power source and small hydropower station
Etc. the wide application prospect of aspect.But in fact, the stability and durability of fuel cell
Always hinder its technological progress, commercialized difficult problems of marching toward.Expand particularly with gas
Dissipate for layer, its composition includes carbon paper or carbon cloth substrate and by carbon dust and polytetrafluoroethylene (PTFE)
(PTFE) microporous layers for constituting, and the meeting under high potential and sour environment of above-mentioned carbon material
Generation oxide etch, generation C-O and C=O functional groups, the oxidation reaction that it occurs is as follows：
C+2H2O→CO2+4H++4e- (0.207V vs.RHE) (1)
C+H2O→CO+2H++2e- (0.518V vs.RHE) (2)
Although the oxide etch reaction rate of carbon material is relatively low under normal circumstances, non-
Can cause cathode potential suddenly higher than open circuit potential in nominal situation such as parking and start-up course,
The electrode potential of this unexpected increase can dramatically speed up the oxide etch speed of carbon material.
Effect of the gas diffusion layers in Proton Exchange Membrane Fuel Cells is concentrated mainly on following four
Individual aspect：1) ensure reaction gas from circulation passage high efficiency of transmission to Catalytic Layer；2) catalysis is made
The aqueous water produced in layer drains into circulation passage；3) electronics is conducted；4) in low-moisture conditions
The wetability of lower holding film.Research report for gas diffusion layers is a lot, but is mostly to close
Influence, the close and distant water process of microporous layers and the corrosion of carbon material in different PTFE treatment
Mechanism etc., seldom relates to the research of Development of Novel microporous layer material or carbon dust substitute.
The content of the invention
It is an object of the invention to provide a kind of novel microporous layer with high electrochemical stability
The preparation method of material.Choose the preferable inorganic oxide particles of electrochemical stability, oxidation
Tin, indium oxide or tin-antiomony oxide, substitute traditional carbon powder material (Vulcan XC-72)；Together
When, in oxide particle surface the carbon coating with high conductivity is constructed to increase inorganic material
Conductive capability, by controlling thickness, the uniformity and the continuity of conductive coating, with reality
Now the nano composite material can possess conduction higher while keeping its electrochemically stable
Ability.This compound is used as new microporous layer material, battery can not only be greatly improved
Durability can also improve the performance of battery.
It is a kind of for inorganic material, simple efficient another object of the present invention is to provide
Method for coating.
To achieve the above object, the technical solution adopted by the present invention can be real by the following method
It is existing：
It is a kind of with high electrochemical stability, the oxidate nano with nitrating carbon coating
Grain preparation method, choose tin oxide, one kind of indium oxide or tin-antiomony oxide be placed on it is carbon containing
In the cushioning liquid of predecessor, at room temperature by the immersion of 20-36h, in pipe after centrifugal drying
Formula stove high temperature is carbonized, finely ground to obtain the nano-complex powder afterwards.
Preferably, described oxide particle is the one of tin oxide, indium oxide or tin-antiomony oxide
Kind, particle size is 4-40nm.
Preferably, described buffer solution system is potassium phosphate,monobasic and dipotassium hydrogen phosphate system
Or Tri(Hydroxymethyl) Amino Methane Hydrochloride cushioning liquid, pH value is 6-9.
Preferably, carbon matrix precursor or covering are glucose, aniline, dopamine or pyrroles
It is a kind of.
The preparation method of nano-complex provided by the present invention, its step is as follows：
1. the cushioning liquid that a certain amount of pH is 6-9 is taken, above-mentioned several inorganic oxides are added
One kind, magnetic agitation makes it be uniformly dispersed；
2. carbon matrix precursor is added to mixed solution system, under moderate strength magnetic agitation, made
Oxide particle is fully coated；
3. after above-mentioned mixed liquor is through high speed centrifugation, done under the conditions of being vacuum dried at 50-80 DEG C
Dry 8-36h, vacuum 0.08MPa；
4. after the solid abrasive that will obtain is uniform, the carbonization of tube furnace high temperature, carbonization are placed in
Temperature be 400-600 DEG C, the time is in 3-6.5h, nitrogen or argon gas atmosphere.
The present invention is a kind of with high electrochemical stability for preparing, with nitrating carbon coating
Oxide nano particles, the oxide for being used is tin oxide, indium oxide and tin-antiomony oxide
One kind, particle size is 4-40nm, the predecessor or covering of carbon are glucose, aniline,
Dopamine or one kind of pyrroles.
The present invention is to choose the more preferable inorganic oxide particles of electrochemical stability to substitute carbon dust,
And construct the coating of high conductivity in the oxide surface.The conductive coating is ensureing material
Original electrochemical stability simultaneously, can assign its more preferable electric conductivity.It is multiple based on the nanometer
Novel cathode gas diffusion layers prepared by compound, show the corrosion resistant higher than commercialization carbon dust
Stability is lost, and battery performance test is also showed that and can be applied to actual potentiality.
The invention has the advantages that：
1. the method for preparing nano-complex particle is simple, is by simple immersion at room temperature
It is capable of achieving.
2. carbon powder material is substituted with electrochemical stability more preferable inorganic oxide particles, effectively
Improve cathode gas diffusion layer resistance high potential and sour environment ability, hence it is evident that improve
The stability and durability of battery.
3. the present invention is carried out at cladding using the coating of high conductivity to inorganic oxide particles
Reason, battery testing is carried out by the final cathode diffusion layer for preparing, and is as a result shown than commercialization
Carbon-based diffusion layer battery performance higher.
Brief description of the drawings
Fig. 1 is the preparation process of nano-complex involved in the present invention.
Fig. 2 is the contact resistance test of novel cathode diffusion layer material involved in the present invention
Figure.
Fig. 3 is nano-complex involved in the present invention before and after constant potential is aoxidized after 2h
CV variation diagrams.
Fig. 4 is novel cathode diffusion layer material involved in the present invention in simulated battery condition
Under, the CV figures before and after 70 DEG C of constant potential oxidation 24h.
Fig. 5 is the battery performance test of novel cathode diffusion layer material involved in the present invention
Figure.
Specific embodiment
The present invention is further described below by way of specific implementation example, but the present invention is not only
It is limited to following embodiment.
Embodiment 1
Weigh 300mg tin-antiomony oxides (ATO) and add PH=7.2 potassium phosphate,monobasics and phosphoric acid
In the buffer system of hydrogen dipotassium, magnetic agitation 30min makes it fully dissolve；It is molten to the mixing
Liquid adds 60mg aniline, at room temperature magnetic agitation 36h；By above-mentioned solution high speed centrifugation four
Secondary, speed setting is 7000r min-1, each time 6min；The sediment that will be centrifuged enters
Row vacuum drying, 70 DEG C of condition, vacuum 0.08MPa dry 12h；Above-mentioned solid is dried
After thing grinding is uniform, the high temperature cabonization in tube furnace is placed in quartz boat, using nitrogen
Protection, heating schedule is set as：160 DEG C of insulation 1h are heated to from 20 DEG C, are reheated
To 500 DEG C of insulation 4h, natural cooling cooling, programmed rate is 5 DEG C of min-1；Will
Can be used to prepare new cathode diffusion layer after above-mentioned solid material is finely ground.
The electrochemistry for testing the nano complexes material using CHI730 electrochemical workstations is steady
Qualitative, (vs NHE) constant potential aoxidizes 2 hours under 1.2V current potentials, and tests oxygen
CV changes before and after changing；Longitudinal direction is carried out to the new diffusion layer material using universal testing machine
Contact resistance is tested；Meanwhile, in order to more accurately investigate the performance of the nano-complex, lead to
Simulated battery environmental condition is crossed, further using channel constant potentiometer to the cathode diffusion layer
Material carries out accelerated corrosion research.Finally, being assembled into monocell carries out battery performance sign,
Cell operating conditions are as follows：Battery temperature is 65 DEG C, 0.05MPa, the lower hydrogen that is humidified entirely,
Oxygen gas flow rate is respectively 50,100ml min-1。
Embodiment 2
Weigh the Tri(Hydroxymethyl) Amino Methane Hydrochloride that 400mg tin oxide adds pH to be 8.0
In cushioning liquid, magnetic agitation makes it fully dissolve；Add 40mg many to the mixed solution
Bar amine, carries out magnetic agitation 24h with moderate strength rotating speed at room temperature；By above-mentioned solution at a high speed
Centrifugation four times, speed setting is 8000r min-1, each time 5min；By above-mentioned centrifugation
Complete sediment is vacuum dried, and 65 DEG C of condition, vacuum 0.08MPa dry 20h；
After the grinding of above-mentioned solid dried object is uniform, the pyrocarbon in tube furnace is placed in quartz boat
Change, protected using argon gas, heating schedule sets ibid embodiment 1；By above-mentioned solid material
Can be used to prepare new cathode diffusion layer after finely ground.Test is characterized with embodiment 1.
Embodiment 3
Weigh the buffer system that 400mg tin oxide adds potassium phosphate,monobasic and dipotassium hydrogen phosphate
In, magnetic agitation 30min；Until completely dissolved to addition 80mg pyrroles in mixed solution,
Magnetic agitation 24h at room temperature；By above-mentioned solution high speed centrifugation four times, speed setting is 9000
r min-1, each time 4min；The complete sediment of above-mentioned centrifugation is vacuum dried, bar
70 DEG C of part, vacuum 0.08MPa dry 12h；After above-mentioned solid dried object grinding is uniform,
The high temperature cabonization in tube furnace is placed in quartz boat, is protected using nitrogen, heating schedule
Set ibid embodiment 1；By above-mentioned solid material it is finely ground after i.e. can be used to prepare new the moon
Pole diffusion layer.Test is characterized with embodiment 1.
Embodiment 4
Take the trihydroxy methyl amino first that 420mg tin-antiomony oxides (ATO) add pH to be 8.5
In heptane hydrochloride salt buffer solution, magnetic agitation 30min makes it fully dissolve；It is molten to the mixing
Liquid adds 30mg dopamines, carries out magnetic agitation 24h with moderate strength rotating speed at room temperature；
By above-mentioned solution high speed centrifugation four times, speed setting is 8000r min-1, each time 5min；
The sediment that will be centrifuged is vacuum dried, and 60 DEG C of condition, vacuum 0.08MPa do
Dry 24h；After the grinding of above-mentioned solid dried object is uniform, it is placed in quartz boat in tube furnace
Interior high temperature cabonization, is protected using argon gas, and heating schedule sets ibid embodiment 1；Will be above-mentioned
Can be used to prepare new cathode diffusion layer after solid material is finely ground.Test is characterized with implementation
Example 1.
Embodiment 5
Take the trishydroxymethylaminomethane that 300mg indium oxides (ATO) add pH to be 9.0
In hydrochloric acid salt buffer solution, magnetic agitation 30min makes it fully dissolve；To the mixed solution
30mg dopamines are added, magnetic agitation 24h is carried out with moderate strength rotating speed at room temperature；Will
Above-mentioned solution high speed centrifugation four times, speed setting is 8500r min-1, each time 5min；
The sediment that will be centrifuged is vacuum dried, and 55 DEG C of condition, vacuum 0.08MPa do
Dry 24h；After the grinding of above-mentioned solid dried object is uniform, it is placed in quartz boat in tube furnace
Interior high temperature cabonization, is protected using argon gas, and heating schedule sets ibid embodiment 1；Will be above-mentioned
Can be used to prepare new cathode diffusion layer after solid material is finely ground.Test is characterized with implementation
Example 1.
The present invention is to choose the more preferable inorganic oxide particles of electrochemical stability to substitute carbon dust,
And construct the coating of high conductivity in the oxide surface.The conductive coating is ensureing material
Original electrochemical stability simultaneously, can assign its more preferable electric conductivity.It is multiple based on the nanometer
Novel cathode gas diffusion layers prepared by compound, show the corrosion resistant higher than commercialization carbon dust
Stability is lost, and battery performance test is also showed that and can be applied to actual potentiality.
Claims (7)
1. a kind of preparation method of microporous layer material, it is characterised in that：Process is as follows
A) inorganic oxide powder is dissolved in the cushioning liquid of pH value 6-9, magnetic agitation
Treat that it fully dissolves；
B) to adding the carbon matrix precursor, carbon matrix precursor to be with oxide powder mass ratio in solution
1:5~1:16, the lower magnetic agitation 24-36h of temperature；
C) above-mentioned solution centrifugal is separated 2-6 times, each 4-6min, rotating speed 7000-9500
r min-1；
D) sediment after being centrifuged is vacuum dried, after being ground with mortar, is placed in tube furnace
High temperature cabonization；
E) grinding of above-mentioned powder sample is uniformly obtained into microporous layer material.
2. according to the preparation method described in claim 1, it is characterised in that：The inorganic oxide
Thing powder is tin oxide, tin-antiomony oxide (SnO2/Sb2O3=90:10), one kind of indium oxide or
More than two kinds of mixture.
3. according to the preparation method described in claim 1, it is characterised in that：The cushioning liquid
It is potassium phosphate,monobasic and dipotassium hydrogen phosphate buffer solution or Tri(Hydroxymethyl) Amino Methane Hydrochloride buffering
Liquid, pH value is between 6-9.
4. according to the preparation method described in claim 1, it is characterised in that：The carbon matrix precursor
It is one or two or more kinds in glucose, aniline, dopamine or pyrroles.
5. according to the preparation method described in claim 1, it is characterised in that：It is vacuum drying
Temperature is 50-80 DEG C, and drying time is between 8-36h.
6. according to the preparation method described in claim 1, it is characterised in that：Tube furnace high temperature
The temperature of carbonization is 400-600 DEG C, and the time, atmosphere was nitrogen or argon gas atmosphere in 3-6.5h.
7. according to the preparation method described in claim 1 or 6, it is characterised in that：Pyrocarbon
Change using nitrogen protection, heating schedule is set as：120-180 DEG C is heated to from 20 DEG C
Insulation 0.5-1.5h, is heated to 400-550 DEG C of insulation 2-6h, natural cooling cooling, journey
Sequence heating rate is 5 DEG C of min-1。
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| CN201510772295.9A CN106711466A (en) | 2015-11-12 | 2015-11-12 | Preparation method of micro-porous layer material |
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| CN201510772295.9A CN106711466A (en) | 2015-11-12 | 2015-11-12 | Preparation method of micro-porous layer material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024066333A1 (en) * | 2022-09-27 | 2024-04-04 | 深圳市贝特瑞新能源技术研究院有限公司 | Carbon material and preparation method therefor, and fuel cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803490A (en) * | 2014-02-27 | 2014-05-21 | 北京化工大学 | Carbon nanofiber material and preparing method and application of carbon nanofiber material |
| CN103972478A (en) * | 2014-05-13 | 2014-08-06 | 北京化工大学 | Hollow carbon nanofiber material as well as preparation method and application thereof |
-
2015
- 2015-11-12 CN CN201510772295.9A patent/CN106711466A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803490A (en) * | 2014-02-27 | 2014-05-21 | 北京化工大学 | Carbon nanofiber material and preparing method and application of carbon nanofiber material |
| CN103972478A (en) * | 2014-05-13 | 2014-08-06 | 北京化工大学 | Hollow carbon nanofiber material as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YONGYI JIANG 等: ""A new microporous layer material to improve the performance and durability of polymer electrolyte membrane fuel cells"", 《RSC ADV》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024066333A1 (en) * | 2022-09-27 | 2024-04-04 | 深圳市贝特瑞新能源技术研究院有限公司 | Carbon material and preparation method therefor, and fuel cell |
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Application publication date: 20170524 |