CN110444769A - A kind of super-hydrophobic gas diffusion layers of high conductivity and preparation method thereof - Google Patents
A kind of super-hydrophobic gas diffusion layers of high conductivity and preparation method thereof Download PDFInfo
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/8605—Porous electrodes
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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
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
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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
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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 present invention relates to fuel cell fields, more particularly, to super-hydrophobic gas diffusion layers of a kind of high conductivity and preparation method thereof.The gas diffusion layers include by hydrophobic treatment porous, electrically conductive base material and the composite microporous layer of super-hydrophobic carbon nanotube/carbon material coated in porous, electrically conductive base material side or to be made from it.Super-hydrophobic carbon nanotube has the conductivity much higher than polytetrafluoroethylene (PTFE), therefore uses super-hydrophobic carbon nanotube that will greatly improve the electric conductivity of microporous layers in gas diffusion layers as hydrophobing agent.Using a kind of not only available super-hydrophobic gas diffusion layers of high conductivity of the present invention, but also its preparation process is not necessarily to high-temperature process, has the characteristics that low energy consumption, environmental protection, has stronger practicability.
Description
Technical field
The present invention relates to fuel cell fields, more particularly, to the gas diffusion layers in fuel cell critical material, especially
It is the microporous layers and preparation method thereof being related in gas diffusion layers.
Technical background
Fuel cell is a kind of power generation that the chemical energy of the fuel such as hydrogen, methanol, ethyl alcohol can be converted directly into electric energy
Device has the characteristics that energy conversion efficiency height, product cleaning.Fuel cell pile is stacked by many monolithic fuel cells
It forms.Monolithic fuel cell is made of intermediate membrane electrode and the bipolar plates that membrane electrode is clipped in the middle, by multiple monolithics
Cell stacks fit together to form fuel cell pile.The composition of membrane electrode be successively from centre to both sides proton exchange membrane,
Catalytic Layer and gas diffusion layers.Gas diffusion layers play the compression for bearing bipolar plates in membrane electrode, protect Catalytic Layer, promote
Gas is uniformly diffused into Catalytic Layer, steam is discharged, the multiple actions such as conduction electric current, are the passes for influencing fuel cell electrode performance
One of key member.
Gas diffusion layers are the supporting layers being made of porous conductive materials such as porous carbon paper, carbon cloth, foaming metals and to lead
Electric carbon black/hydrophobing agent coats the microporous layers to be formed and collectively constitutes.Since fuel cell can generate water in cathode at work, if not
Discharge in time is flooded to reduce fuel battery performance it will cause Catalytic Layer.Hydrophobic surface is not easy to adsorb water, enables water to
Quickly discharge, it is therefore desirable to which hydrophobic treatment is carried out to porous support layer and microporous layers.
In the prior art, it is to the usual way of the preparation of microporous layers in gas diffusion layers: by conductive black, carbon dust etc.
It is coated on the branch Jing Guo hydrophobic treatment by techniques such as spraying, blade coating, silk-screen printings after mixing in a solvent with hydrophobing agent
It supports on layer, handles certain time under high temperature (350 DEG C or so) again after drying, hydrophobic gas diffusion layer is finally obtained, referring to hair
Zong Qiang edits " fuel cell ".
Chinese invention patent application number 200610047931.2 (a kind of gas diffusion layer for fuel cell and its preparation) will
Acetylene black is coated on carbon paper or carbon cloth through hydrophobic treatment after mixing with hydrophobing agent, then passes through 150~280 DEG C of heating,
10~100min of roast obtains hydrophobic gas diffusion layer at 300~400 DEG C again, wherein hydrophobing agent dosage reach 10%~
30%.
A kind of (the super-hydrophobic gas diffusion of fuel cell durability of Chinese invention patent application number 201810493251.6
Layer) by mass fraction be respectively 3-4:1-2:10-15 conductive agent, hydrophobic microballoon and binder mix after be coated on hydrophobic treatment
Carbon paper on, at 270-380 DEG C, be passed through protective gas and handle to obtain hydrophobic treatment gas diffusion through 20-30min firing
Layer.The patent the method improves the surface flatness and flatness of microporous layers.
In the prior art, hydrophobing agent generallys use polytetrafluoroethylene (PTFE) (PTFE), inclined tetrafluoroethene (PVDF) or fluorinated ethylene-propylene
The fluoropolymers or polymethyl siloxane etc. such as alkene (FEP) have hydrophobic high molecular material.But due to these hydrophobing agents
Non-conductive (conductivity < 10 itself-14S/cm), the electric conductivity of gas diffusion layers can be made to reduce using these hydrophobing agents.
Carbon nanotube has high specific surface area, high thermal conductivity rate, electrochemical corrosion resistant and excellent mechanical property
Can, it can be applied to the electrode material etc. of supercapacitor and lithium ion battery.In order to which carbon nanotube is applied to more scenes,
Carrying out hydrophobically modified to carbon nanotube also has more report.Such as multi-walled carbon nanotube modification is connect using octadecylamine
The ultra-hydrophobic conductive carbon nanotube that feeler is 165 °, conductivity is 11.3 S/cm, referring to Yao H, Chu C C, Sue H J, et
al.Electrically conductive superhydrophobic octadecylamine-functionalized
multiwall carbon nanotube films[J].Carbon,2013, 53:366-373；Multi-walled carbon nanotube grafting contains
It is 157.7 ° that fluoropolymer, which obtains contact angle when the mass ratio of carbon nanotube and polymer is 10:3, referring to Soojin P,
Longyue M.Improvement of Superhydrophobicity of Multi-Walled Carbon Nanotubes
Produced by Fluorination[J]. Carbon Letters,2012,13(3):178-181。
Although disclosing the preparation method of super-hydrophobic carbon nanotube as described above in the prior art, have no in fuel electricity
Application in the gas diffusion layers of pond, and in the prior art, also there is not yet open report that super-hydrophobic carbon nanotube coats carbon material
The method for preparing gas diffusion layers.
In the prior art, the microporous layers in gas diffusion layers are to use nonconducting hydrophobic polymer and conductive carbon material
High-temperature process is prepared after mixing, this can reduce the electric conductivity of gas diffusion stratification, and high-temperature process compares energy consumption；In addition, micro-
The carbon-based conductive agents such as conductive carbon black interact weaker with high molecular hydrophobic agent in aperture layer preparation process, so as to cause point of the two
Unevenness is dissipated, forming aggregation reduces hydrophobic uniformity.
The applicant has found by groping repeatedly with many experiments, utilizes the fiber properties of carbon nanotube and itself and carbon materials
The strong interaction of material, carbon nanotube can closely wind carbon-based conductive particle, to reduce the dosage of binder, and prepare
Journey does not need high-temperature process.In addition, the conductivity (> 10 of super-hydrophobic carbon nanotube-4S/cm it) is substantially higher in PTFE (< 10-14
The polymer such as S/cm) use super-hydrophobic carbon nanotube that can significantly improve gas diffusion layers as hydrophobing agent preparation microporous layers
Electric conductivity.
Summary of the invention
An object of the present invention is to provide a kind of super-hydrophobic gas diffusion layers of high conductivity, and the gas diffusion layers have
High conductivity and super-hydrophobicity.
It is a further object of the present invention to provide the method for preparing the super-hydrophobic gas diffusion layers of the high conductivity, the methods
Has the characteristics that preparation process energy conservation and environmental protection.
It is yet another object of the invention to provide the fuel cells for using the super-hydrophobic gas diffusion layers of high conductivity of the present invention.
To achieve the goals above, the invention adopts the following technical scheme.
One of technical solution of the present invention is to provide a kind of super-hydrophobic gas diffusion layers of fuel cell high conductivity, includes
Hydrophobic treatment porous, electrically conductive base material and super-hydrophobic carbon coated in the hydrophobic treatment porous, electrically conductive base material side are received
The composite microporous layer of mitron/carbon material.
In one embodiment, the super-hydrophobic gas diffusion layers of the high conductivity are by hydrophobic treatment porous, electrically conductive substrate material
Material and the composite microporous layer group of super-hydrophobic carbon nanotube/carbon material coated in the hydrophobic treatment porous, electrically conductive base material side
At.
In one embodiment, the super-hydrophobic carbon nanotube be using containing epoxy or carboxyl carbon nanotube with containing-
NH2The product of the organic compound reaction of group.Can be commercially available or using carbon nanotube voluntarily modified preparation, it will such as contain-NH2
Primary amine organic matter/ethanol solution of group is mixed with carbon nanotube/aqueous dispersions containing epoxy group, is reacted at 80~90 DEG C
Certain time obtains hydrophobically modified carbon nano tube products.Method of modifying is the disclosed prior art, referring to: Yao H, Chu C
C,Sue H J,et al.Electrically conductive superhydrophobic octadecylamine-
functionalized multiwall carbon nanotube films[J]. Carbon,2013,53:366-373；
Yong T,Gou J,Yuan H.Covalent functionalization of carbon nanotubes with
polyhedral oligomeric silsequioxane for superhydrophobicity and flame
retardancy[J].Polymer Engineering&Science,2013,53(5):1021-1030。
Selectable, described contains-NH2The organic compound of group is selected from one of following compounds or a variety of: just
Heptyl amice, 2- cyclopenta ethamine, 2- amino-octane, 2- amino -6- methyl heptane, 1- amino -6- methyl heptane, 2 ethyl hexylamine,
2- cyclohexylethylamine, n-hexylamine, octane amine, 2- amino nonane, positive nonyl amine, 1- decyl amine, positive undecylamine, 2- ammonia hendecane, 12
Amine, tridecyl amine, tetradecy lamine, pentadecyl amine, cetylamine, heptadecyl-amine, octadecylamine, 19 amine, 20 amine, aniline, toluidines, benzene second
Amine, to Methylphenethylamine, 3- phenylpropylamine, ethylenediamine, 2- methyl-1,5- 1,5-DAP, 1,6- hexamethylene diamine, 1,7- heptan two
Amine, 1,8- octamethylenediamine, 1,9- nonamethylene diamine, 1,10- decamethylene diamine, 1,11- diamino undecane, 1,12- diamino dodecane, 1,
Six alkane of 16- diamino, 5- (dimethylamino) amylamine, 3- (dibutylamino) propylamine.
It is preferred that n-hexylamine, octane amine, 2- amino nonane, positive nonyl amine, 1- decyl amine, positive undecylamine, 2- ammonia hendecane, 12
Amine, tridecyl amine, tetradecy lamine, pentadecyl amine, cetylamine, heptadecyl-amine, octadecylamine, 19 amine, 20 amine, 1,7- heptamethylene diamine, 1,8- are pungent
Diamines, 1,9- nonamethylene diamine, 1,10- decamethylene diamine, 1,11- diamino undecane, 1,12- diamino dodecane, 1,16- diamino
One of six alkane are a variety of, more preferable tridecyl amine, tetradecy lamine, pentadecyl amine, cetylamine, heptadecyl-amine, octadecylamine, 19 amine, two
One of ten amine, 1,12- diamino dodecane, six alkane of 1,16- diamino are a variety of.
It should be understood that can be used for of the invention containing-NH2The organic compound of group is not limited to above-named organic
Compound, those skilled in the art can select other suitably to contain-NH as the case may be2The organic compound of group, and
Without departing from protection scope of the present invention.
It is selectable, it is above-mentioned to contain-NH in the super-hydrophobic carbon nanotube2The organic compound of group accounts for carbon modified and receives
The 15%~45% of mitron quality, preferably 20~45%, more preferable 28~40%, more preferably, 29%, 30%, 31%,
32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%.
In one embodiment, the super-hydrophobic carbon nanotube is the product of carbon nanotube grafted hydrophobic polymer, can
To be made by the following method: by carbon nanotube in H2SO4/HNO3Middle oxidation obtains carboxylic acid carbon nano tube, then anti-with sulfonic acid chloride
Acyl chlorides carbon nano tube should be obtained, acyl chlorides carbon nano tube can obtain hydrophobic conductive carbon nanotube with the hydrophobic polymer of amino-contained
Pipe, grafting method are the disclosed prior art, referring to: Yong T, Gou J, Yuan H.Covalent
functionalization of carbon nanotubes with polyhedral oligomeric
silsequioxane for superhydrophobicity and flame retardancy[J].Polymer
Engineering&Science,2013,53(5):1021-1030。
In one embodiment, the super-hydrophobic carbon nanotube can also obtain by the following method: nanotube is set
Reflux obtains hydroxyl carbon nanotube in hydrogen peroxide, and fluoropolymer is grafted to hydroxyl carbon nano tube with silane coupling agent
On obtain ultra-hydrophobic conductive carbon nanotube, referring to Meng L Y, Park S J.Effect of fluorination of
carbon nanotubes on superhydrophobic properties of fluoro-based films[J]
.Journal of Colloid&Interface Science,2010,342(2):559-563；Soojin P, Longyue
M.Improvement of Superhydrophobicity of Multi-Walled Carbon Nanotubes
Produced by Fluorination[J].Carbon Letters,2012,13(3):178-181。
Optionally, the hydrophobic polymer is the polymethyl siloxane of amino-contained functional group, cage modle polysilsesquioxane, gathers
One of isobutene, polystyrene, fluoropolymer including polytetrafluoroethylene (PTFE), Kynoar, fluorinated acrylamide etc.
Or it is a variety of.It is preferred that the polymethyl siloxane of amino-contained functional group, cage modle polysilsesquioxane, polyisobutene, polystyrene, poly- four
Vinyl fluoride.Polymethyl siloxane, the cage modle polysilsesquioxane, polytetrafluoroethylene (PTFE) of more preferable amidine functional group.
It should be understood that may be used as hydrophobic polymer of the invention is not limited to above-named, those skilled in the art
Other suitable hydrophobic polymers can be selected as the case may be, without beyond the scope of the present invention.
Optionally, the polymer being grafted in the carbon nanotube accounts for the 20~85% of super-hydrophobic carbon nanotubes, preferably
25~75%, more preferable 30~60%, more preferably, 40~50% or 41%, 42%, 43%, 44%, 45%, 46%,
47%, 48%, 49%.
Optionally, the degree of polymerization of the polymer is 15~450, preferably 45~350, more preferable 80~270, further preferably
Ground, 100-200.
Optionally, carbon nanotube be single wall or multi-walled carbon nanotube, draw ratio be 20:1~100:1, preferably 30:1~
90:1, more preferable 50:1~85:1.
Optionally, the conductive carbon material be electrical conductivity Carbon black, active carbon, carbosphere, carbon whisker, graphite powder, acetylene black,
One of graphene or carbon fiber or a variety of mixing.
Optionally, the partial size of the conductive carbon material particle be 0.01~1.3 μm, preferably 0.05~0.7 μm, more preferably
0.1~0.5 μm.
Another technical solution of the invention is to provide a kind of method for preparing the super-hydrophobic gas diffusion layers of high conductivity,
It is characterized in that, described method includes following steps:
(1) super-hydrophobic carbon nanotube is added in organic solvent, it is 0.1~3.0 mg/ that ultrasound, which obtains concentration, after stirring
Super-hydrophobic carbon nanotube/dispersion in organic solvent of mL；
(2) carbon material is slowly added into above-mentioned super-hydrophobic carbon nanotube/dispersion in organic solvent, and be stirred continuously so
Ultrasonic disperse afterwards, then binder is slowly added dropwise and is sufficiently stirred, obtain super-hydrophobic carbon nanotube/carbon material compound slurry；
(3) above-mentioned slurries are coated on to the side of the porous, electrically conductive base material through hydrophobic treatment, then at 60~80 DEG C
It is dry in lower vacuum drying oven.
In step (1), the concentration preferably 0.3~2.5mg/mL, more preferable 0.5~2.0mg/mL.
In step (1), in the super-hydrophobic carbon nano tube/conducting carbon material compound slurry, solid content be 1%~
45%, preferably 2~35%, more preferable 5~25%；The super-hydrophobic carbon nano-tube material accounts for the 1~15% of total solids content, excellent
Select 2~12%, more preferable 4~9.5%；The consumption of binder accounts for the 0.1~7% of total solids content, preferably 0.3~5.5%,
More preferable 0.7~3.5%.
In step (1), the organic solvent be ethyl alcohol or isopropanol or other.
In step (2), the carbon material is conductive carbon material.
In step (2), the binder be Kynoar (PVDF) or butadiene-styrene rubber (SBR) lotion or other.
In step (3), the coating is that spraying, blade coating, spin coating, slit extrusion coated, electrostatic spinning or transfer etc. apply
One of mode for cloth.
Another technical solution of the invention is to provide a kind of fuel cell, and the fuel cell uses above-mentioned high conductivity
Super-hydrophobic gas diffusion layers or the super-hydrophobic gas diffusion layers of high conductivity of above method preparation.
Use scope of the invention is not limited to any fuel cell.Currently, type of fuel cell known to having 5 kinds, name
Claim related with the corresponding electrolyte used.
(1) alkaline fuel cell (AFC) --- using potassium hydroxide solution as electrolyte；
(2) Proton Exchange Membrane Fuel Cells (PEMFC) --- using very thin polymer dielectric film as its electrolyte；
(3) phosphoric acid fuel cell (PAFC) --- using the phosphoric acid under 200 DEG C of high temperature as its electrolyte；
(4) carbonate fuel cell (MCFC) is melted --- using sodium carbonate or potassium carbonate as electrolyte；
(5) solid-state oxygen fuel cell (SOFC) --- use solid electrolyte.
The utility model has the advantages that
Compared with prior art using the technology of the present invention, the feature and excellent effect protruded is:
(1) high conductivity is had by using super-hydrophobic carbon nanotube and the microporous layers of the compound preparation of conductive carbon material；
(2) providing gas diffusion layers and preparation method thereof can avoid gas diffusion layers high-temperature process, reduce preparation
Energy consumption in the process；
Specific embodiment:
Below with reference to embodiment, the present invention is further described, but does not constitute limiting the scope of the invention.Unless
In addition illustrate, following materials are used for embodiment described below.
Infrared (FT-IR) test, using Nicolet company, U.S. Nexsus 6700-FT-IR, ATR, scanning range:
4000cm-1~400cm-1。
Thermogravimetric test uses TA company, U.S. Q50 nitrogen atmosphere with the heating rate of 10 DEG C/min from 25~600 DEG C.
Water contact angle test: contact angle system OCA (dataphysics) measuring instrument is used, with 5 μ L's
Drop amount carries out testing film surface, and each sample is tested 5 times and is averaged.
Membrane electrode performance test: it is polarized using scribner company, U.S. 890e Fuel Cell Test Loads
Curve and ac impedance measurement.
The super-hydrophobic gas diffusion layers of high conductivity of the invention are generally prepared using following methods:
(1) super-hydrophobic carbon nanotube is added in ethyl alcohol or isopropanol first, it is ultrasonic that super-hydrophobic carbon is received by stirring
Mitron dispersion liquid；
(2) conductive carbon particle is slowly added into above-mentioned super-hydrophobic carbon nano tube dispersion liquid, and be stirred continuously, ultrasound point
It dissipates, Kynoar (PVDF) or butadiene-styrene rubber (SBR) lotion is then slowly added dropwise as binder and is sufficiently stirred, is surpassed
Hydrophobic carbon nanotube/conductive carbon material compound slurry；
(3) above-mentioned slurries are passed through into the coating methods such as spraying, blade coating, spin coating, slit extrusion coated, electrostatic spinning or transfer
One of be coated on the side of the porous, electrically conductive base material that hydrophobic treatment is crossed；
(4) then dry in vacuum drying oven, obtain the super-hydrophobic gas diffusion layers of high conductivity.
Embodiment 1:
(1) super-hydrophobic carbon nanotube preparation: by 150mg multi-walled carbon nanotube (draw ratio: 100:1) in 300mL water,
Carbon nanotube/aqueous dispersions that concentration is 0.5mg/mL are made in ultrasonic disperse.750mg octadecylamine is dissolved in 30mL ethyl alcohol
In, octadecylamine/ethanol solution of 25mg/mL is made.Carbon nanotube/water dispersion that octadecylamine/ethanol solution is added to
In liquid, 2h is stirred at reflux at 80 DEG C.It filters, filter residue is washed in ethanol, drying for 24 hours, obtains 18 in a vacuum drying oven
The modified oxidized carbon nanotube of alkanamine (CNT-ODA), through TGA test, wherein octadecylamine content is 15%.Take 50mg CNT-ODA
It is scattered in 50mL isopropanol, dispersion liquid concentration 1.0mg/mL；
(2) conductive black that average grain diameter is 1.3 μm is slowly added into super-hydrophobic carbon nano tube dispersion liquid in step (1)
In, and it is stirred continuously then ultrasonic disperse, Kynoar PVDF is then slowly added dropwise as binder and is sufficiently stirred, obtains
Super-hydrophobic carbon nano tube/conducting carbon material compound slurry.The concentration for adjusting slurry makes the super-hydrophobic carbon nano tube/conducting carbon materials
Expect that solid content is 5% in compound slurry, super-hydrophobic carbon nano-tube material accounts for the 4% of total solids content, and consumption of binder Zhan is total
The 3% of solid content；
(3) above-mentioned slurries are sprayed on to the side of the porous, electrically conductive base material of (2) described super-hydrophobic carbon nanotube cladding.
Then dry in vacuum drying oven at 60 DEG C, obtain highly conductive hydrophobic gas diffusion layer.
Gas diffusion layer material obtained in the embodiment of the present invention is subjected to hydrophobicity, electric conductivity and fuel battery performance
Test.Fuel battery performance test is that gained gas diffusion layers in embodiment and catalysis and proton exchange membrane are prepared into membrane electrode
The specific method is as follows: take a certain amount of Pt/C catalyst that beaker is added, be added a small amount of water and isopropanol be dispersed with stirring after be added
Nafion solution obtains the catalyst pulp that concentration is 2%, and the catalyst pulp prepared is sprayed on 212 film of Nafion, is made
The catalyst loading of proton exchange membrane cathode and anode is respectively 0.5mg/cm2And 0.1mg/cm2, the gas diffusion that will prepare
Hot pressing 2min obtains membrane electrode to the film of layer and spraying catalyst at 135 DEG C on flat-bed press.Membrane electrode is placed in fuel electricity
In the fixture of pond pond, monocell performance test is carried out using fuel battery test system, test result is as shown in table 1.
Embodiment 2:
(1) preparation process of super-hydrophobic carbon nanotube is same as Example 1, and only used carbon nanotube draw ratio is
The content of octadecylamine is 28% in 50:1, CNT-ODA, dispersion liquid concentration 0.1mg/mL；
(2) conductive black that average grain diameter is 0.5 μm is slowly added into super-hydrophobic carbon nano tube dispersion liquid in step (1)
In, and it is stirred continuously then ultrasonic disperse, Kynoar PVDF is then slowly added dropwise as binder and is sufficiently stirred, obtains
Super-hydrophobic carbon nano tube/conducting carbon material compound slurry.The concentration for adjusting slurry makes the super-hydrophobic carbon nano tube/conducting carbon materials
Expect that solid content is 1% in compound slurry, super-hydrophobic carbon nano-tube material accounts for the 1% of total solids content, and consumption of binder Zhan is total
The 7% of solid content；
(4) same as Example 1.
Hydrophobicity, electric conductivity and fuel battery performance test are same as Example 1.
Embodiment 3:
(1) preparation process of super-hydrophobic carbon nanotube is same as Example 1, and only used carbon nanotube draw ratio is
The content of octadecylamine is 45% in 30:1, CNT-ODA, dispersion liquid concentration 2.0mg/mL；
(2) conductive black that average grain diameter is 0.3 μm is slowly added into super-hydrophobic carbon nano tube dispersion liquid in step (1)
In, and it is stirred continuously then ultrasonic disperse, Kynoar PVDF is then slowly added dropwise as binder and is sufficiently stirred, obtains
Super-hydrophobic carbon nano tube/conducting carbon material compound slurry.The concentration for adjusting slurry makes the super-hydrophobic carbon nano tube/conducting carbon materials
Expect that solid content is 15% in compound slurry, super-hydrophobic carbon nano-tube material accounts for the 7% of total solids content, and consumption of binder Zhan is total
The 1% of solid content；
(4) above-mentioned slurries are coated in the porous, electrically conductive substrate of (2) the super-hydrophobic carbon nanotube cladding using knife coating
The side of material.Then dry in vacuum drying oven at 60 DEG C, obtain highly conductive hydrophobic gas diffusion layer.
Hydrophobicity, electric conductivity and fuel battery performance test are same as Example 1.
Embodiment 4:
(1) multi-walled carbon nanotube (MWCNT, draw ratio 90:1) 5g super-hydrophobic carbon nanotube preparation: is added to sulfuric acid:
Nitric acid is ultrasound 2h at 40 DEG C in the mixed acid of 3:1, and then at 60 DEG C after reflux 2h, filtering and washing to neutrality obtains Carboxylation
Carbon nanotube.It takes 0.3g carboxylation carbon nanotube to be scattered in a large amount of thionyl chloride, 4 drop n,N-Dimethylformamide ultrasounds is added
For 24 hours, then revolving removes thionyl chloride to back flow reaction and solvent obtains acyl chlorides carbon nano tube at 70 DEG C after dispersion.Take 0.3g
Acyl chlorides carbon nano tube and 3g amido polymethyl siloxane (NH2- PDMS, the degree of polymerization 15) and 1ml triethylamine in chloroform
Middle ultrasonic disperse 2h takes out after then reacting 48h at 70 DEG C, and filtering and washing obtains carbon nanotube graft polysiloxane CNT-g-
PDMS.Product, which is scattered in isopropanol, saves dispersion liquid concentration as 0.5mg/mL.Through TGA test, wherein PDMS content is 20%；
(2) graphite powder that average grain diameter is 0.7 μm is slowly added into super-hydrophobic carbon nano tube dispersion liquid in step (1)
In, and it is stirred continuously then ultrasonic disperse, Kynoar PVDF is then slowly added dropwise as binder and is sufficiently stirred, obtains
Super-hydrophobic carbon nano tube/conducting carbon material compound slurry.The concentration for adjusting slurry makes the super-hydrophobic carbon nano tube/conducting carbon materials
Expect that solid content is 2% in compound slurry, super-hydrophobic carbon nano-tube material accounts for the 2% of total solids content, and consumption of binder Zhan is total
The 5% of solid content；
(3) above-mentioned slurries are coated in the porous, electrically conductive of (2) the super-hydrophobic carbon nanotube cladding by way of spraying
The side of base material.Then dry in vacuum drying oven at 60 DEG C, obtain highly conductive hydrophobic gas diffusion layer.
Hydrophobicity, electric conductivity and fuel battery performance test are same as Example 1.
Embodiment 5:
(1) super-hydrophobic preparation method of carbon nano-tube is same as Example 4, and only carbon nanotube draw ratio is 85:1, used
The degree of polymerization of PDMS is that 80, PDMS content is 32%, dispersion liquid concentration 0.5mg/mL；
(2) conductive black that average grain diameter is 0.1 μm is slowly added into super-hydrophobic carbon nano tube dispersion liquid in step (1)
In, and it is stirred continuously then ultrasonic disperse, Kynoar PVDF is then slowly added dropwise as binder and is sufficiently stirred, obtains
Super-hydrophobic carbon nano tube/conducting carbon material compound slurry.The concentration for adjusting slurry makes the super-hydrophobic carbon nano tube/conducting carbon materials
Expect that solid content is 25% in compound slurry, super-hydrophobic carbon nano-tube material accounts for the 9.5% of total solids content, and consumption of binder accounts for
The 0.5% of total solids content；
(3) above-mentioned slurries are coated in the porous, electrically conductive of (2) the super-hydrophobic carbon nanotube cladding by way of blade coating
The side of base material.Then dry in vacuum drying oven at 80 DEG C, obtain highly conductive hydrophobic gas diffusion layer.
Hydrophobicity, electric conductivity and fuel battery performance test are same as Example 1.
Embodiment 6:
(1) super-hydrophobic preparation method of carbon nano-tube is same as Example 4, and only the draw ratio of carbon nanotube is 30:1, institute
It is 270, PDMS content with the polymer of PDMS is 76%, dispersion liquid concentration 1.0mg/mL；
(2) conductive black that average grain diameter is 0.05 μm super-hydrophobic carbon nanotube in step (1) is slowly added into disperse
In liquid, and it is stirred continuously then ultrasonic disperse, Kynoar PVDF is then slowly added dropwise as binder and is sufficiently stirred, obtains
To super-hydrophobic carbon nano tube/conducting carbon material compound slurry.The concentration for adjusting slurry makes the super-hydrophobic carbon nano tube/conducting carbon
Solid content is 30% in Material cladding slurries, and super-hydrophobic carbon nano-tube material accounts for the 12% of total solids content, consumption of binder
Account for the 0.3% of total solids content；
(3) above-mentioned slurries are coated in (2) described super-hydrophobic carbon nanotube cladding by way of slit extrusion coated
The side of porous, electrically conductive base material.Then dry in vacuum drying oven at 80 DEG C, obtain highly conductive hydrophobic gas diffusion layer.
Hydrophobicity, electric conductivity and fuel battery performance test are same as Example 1.
Embodiment 7:
(1) super-hydrophobic preparation method of carbon nano-tube is same as Example 4, and only the draw ratio of carbon nanotube is 20:1, institute
It is 450, PDMS content with the polymer of PDMS is 85%, dispersion liquid concentration 3.0mg/mL；
(2) conductive black that average grain diameter is 0.01 μm super-hydrophobic carbon nanotube in step (1) is slowly added into disperse
In liquid, and it is stirred continuously then ultrasonic disperse, Kynoar PVDF is then slowly added dropwise as binder and is sufficiently stirred, obtains
To super-hydrophobic carbon nano tube/conducting carbon material compound slurry.The concentration for adjusting slurry makes the super-hydrophobic carbon nano tube/conducting carbon
Solid content is 40% in Material cladding slurries, and super-hydrophobic carbon nano-tube material accounts for the 15% of total solids content, consumption of binder
Account for the 0.1% of total solids content；
(4) above-mentioned slurries are coated in (2) described super-hydrophobic carbon nanotube cladding by way of slit extrusion coated
The side of porous, electrically conductive base material.Then dry in vacuum drying oven at 80 DEG C, obtain highly conductive hydrophobic gas diffusion layer.
Hydrophobicity, electric conductivity and fuel battery performance test are same as Example 1.
Comparative example 1:
(1) Toray TGP-H060 carbon paper is impregnated into the PTFE emulsion that concentration is 10%, takes out drying, impregnates again
After dry, then in the case where 350 DEG C of argon gas are protected, annealing 1h obtains the carbon paper of hydrophobic treatment；
(2) 450mg conductive black (0.5 μm of average grain diameter) is taken, is added in 500mg 10%PTFE lotion, PTFE accounts for solid
The 10% of content, a certain amount of isopropanol, which is added, makes the solid content 30% of slurry, and simultaneously ultrasonic disperse makes PTFE to mechanical stirring
It is evenly dispersed in carbon dust, slurry is made；
(3) above-mentioned slurries are coated in the side of (1) described hydrophobic treatment carbon paper by way of slit extrusion coated.So
It is dry in vacuum drying oven at 80 DEG C afterwards, by the gas diffusion layers after drying in the lower 1h that anneals of 350 DEG C of argon gas protections, obtain gas
Diffusion layer.
Hydrophobicity, electric conductivity and fuel battery performance test are same as Example 1.
Table 1
Remarks:*Hydrophobing agent is super-hydrophobic carbon nanotube, binder PVDF in embodiment；PTFE is hydrophobic in comparative example
Agent, while there is PTFE caking property to also function as binder.
As can be seen from the table, super-hydrophobic carbon nanotube and the total amount of binder used in Examples 1 to 5 are less than or equal to comparison
Example 1, but contact angle is all larger than 150 ° and is higher than comparative example 1, that is to say, that use less super-hydrophobic carbon nanotube and binder
It just can exceed that the hydrophobicity for using PTFE as hydrophobing agent and binder；And conductivity is 3 times of comparative example 1 or more.Illustrate benefit
The super-hydrophobic gas diffusion layers of performance more preferably high conductivity compared with prior art can be prepared with the present invention.
The above is only specific embodiments of the present invention, not does limitation in any form to the present invention, though
So the present invention is disclosed as above with specific embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
Member, in the range of not departing from technical solution of the present invention, when using technology contents disclosed above make it is a little change or repair
Decorations are the equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, technology according to the present invention are real
Matter any simple modification, equivalent change and modification to the above embodiments, still fall within the range of technical solution of the present invention
It is interior.
Claims (12)
1. a kind of super-hydrophobic gas diffusion layers of fuel cell high conductivity, it is characterised in that: include hydrophobic treatment porous, electrically conductive
Base material and super-hydrophobic carbon nanotube/carbon material coated in the hydrophobic treatment porous, electrically conductive base material side are compound micro-
Aperture layer.
2. the super-hydrophobic gas diffusion layers of high conductivity according to claim 1, it is characterised in that: the super-hydrophobic carbon nanometer
Pipe is using the carbon nanotube containing epoxy or carboxyl and containing-NH2The product of the organic compound reaction of group, it is described to contain-NH2Base
The organic compound of group is selected from one of following compounds or a variety of: positive heptyl amice, 2- cyclopenta ethamine, 2- amino-octane, 2-
Amino -6- methyl heptane, 1- amino -6- methyl heptane, 2 ethyl hexylamine, 2- cyclohexylethylamine, n-hexylamine, octane amine, 2- ammonia
Base nonane, positive nonyl amine, 1- decyl amine, positive undecylamine, 2- ammonia hendecane, lauryl amine, tridecyl amine, tetradecy lamine, pentadecyl amine, cetylamine,
Heptadecyl-amine, octadecylamine, 19 amine, 20 amine, aniline, toluidines, phenyl ethylamine, to Methylphenethylamine, 3- phenylpropylamine, second two
Amine, 2- methyl-1,5- 1,5-DAP, 1,6- hexamethylene diamine, 1,7- heptamethylene diamine, 1,8- octamethylenediamine, 1,9- nonamethylene diamine, 1, the 10- last of the ten Heavenly stems
Diamines, 1,11- diamino undecane, 1,12- diamino dodecane, six alkane of 1,16- diamino, 5- (dimethylamino) amylamine, 3-
(dibutylamino) propylamine.
3. the super-hydrophobic gas diffusion layers of high conductivity according to claim 2, it is characterised in that: received in the super-hydrophobic carbon
It is described to contain-NH in mitron2The organic compound of group accounts for the 15~45% of the super-hydrophobic carbon nanotube mass.
4. the super-hydrophobic gas diffusion layers of high conductivity according to claim 1, it is characterised in that: the super-hydrophobic carbon nanotube
For the product containing epoxy group or carboxyl carbon nanotube grafted hydrophobic polymer, the hydrophobic polymer is selected from methyl polysilicone
Alkane, cage modle polysilsesquioxane, polyisobutene, polystyrene, polytetrafluoroethylene (PTFE), Kynoar, one in polyhexafluoropropylene
Kind is a variety of.
5. the super-hydrophobic gas diffusion layers of high conductivity according to claim 4, it is characterised in that: the super-hydrophobic carbon nanometer
The degree of polymerization for the hydrophobic polymer being grafted on pipe is 15~450, and accounts for the 20~85% of the super-hydrophobic carbon nanotubes.
6. the super-hydrophobic gas diffusion layers of high conductivity according to claims 1 to 5, it is characterised in that: the carbon nanotube
For single wall or multi-walled carbon nanotube, draw ratio is 20:1~100:1.
7. high conductivity hydrophobic gas diffusion layer according to claim 1, it is characterised in that: the carbon material is conductive carbon
One of black, active carbon, carbosphere, carbon whisker, graphite powder, acetylene black, graphene or carbon fiber or a variety of mixing, it is described
The partial size of carbon material is 0.01~1.30 μm.
8. high conductivity hydrophobic gas diffusion layer according to claim 1, it is characterised in that: the porous, electrically conductive substrate material
Expect one of the carbon paper crossed for hydrophobic treatment, carbon cloth, carbon felt, foaming metal, porous metals or a variety of.
9. a kind of method for preparing the super-hydrophobic gas diffusion layers of high conductivity, which is characterized in that described method includes following steps:
(1) super-hydrophobic carbon nanotube is added in organic solvent, it is the super of 0.1~3.0mg/mL that ultrasound, which obtains concentration, after stirring
Hydrophobic carbon nanotube/dispersion in organic solvent；
(2) carbon material is slowly added into above-mentioned super-hydrophobic carbon nanotube/dispersion in organic solvent, and be stirred continuously then super
Sound dispersion, then binder is slowly added dropwise and is sufficiently stirred, obtain super-hydrophobic carbon nanotube/carbon material compound slurry；
(3) above-mentioned slurries are coated on by spraying, blade coating, spin coating, slit extrusion coated, electrostatic spinning or print-on coating mode
The side of the porous, electrically conductive base material of hydrophobic treatment, it is then dry in vacuum drying oven at 60~80 DEG C.
10. according to the method described in claim 9, it is characterized by: the super-hydrophobic carbon nano tube/conducting carbon material composite pulp
In liquid, solid content is 1%~45%, and the super-hydrophobic carbon nano-tube material accounts for the 1~15% of total solids content, the bonding
Agent dosage accounts for the 0.1~7% of total solids content.
11. according to the method described in claim 9, it is characterized by: the organic solvent is ethyl alcohol or isopropanol, the carbon materials
Material is one of conductive carbon black, active carbon, carbosphere, carbon whisker, graphite powder, acetylene black, graphene or carbon fiber or a variety of
Mixing, the partial size of the carbon material is 0.01~1.30 μm, and the binder is Kynoar (PVDF) or butadiene-styrene rubber
(SBR) lotion.
12. a kind of fuel cell, it is characterised in that: the fuel cell is led using the height of any of claims 1-8
The super-hydrophobic gas of high conductivity of method preparation described in any one of electrically super-hydrophobic gas diffusion layers or claim 9-11
Diffusion layer.
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| CN112259746A (en) * | 2020-10-19 | 2021-01-22 | 成都新柯力化工科技有限公司 | Metal tin bonded fuel cell flexible gas diffusion membrane and preparation method thereof |
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