CN109608794A - PTFE microporous barrier and preparation method thereof and compound proton exchange membrane - Google Patents
PTFE microporous barrier and preparation method thereof and compound proton exchange membrane Download PDFInfo
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- CN109608794A CN109608794A CN201811462976.5A CN201811462976A CN109608794A CN 109608794 A CN109608794 A CN 109608794A CN 201811462976 A CN201811462976 A CN 201811462976A CN 109608794 A CN109608794 A CN 109608794A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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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 discloses a kind of preparation methods of PTFE microporous barrier, steps are as follows: (1) being mixed and stirred for uniformly PTFE powder, auxiliary agent oil and surfactant, be then prepared into the calendering band containing surfactant after curing, striking adobe, pushing calendering；Auxiliary agent oil can be gasoline, aviation kerosine etc..(2) calendering band is stretched through three steps, obtains PTFE microporous barrier after sintering sizing.In the method, the step of being stretched using three steps, i.e. first transverse pre-tension, again longitudinal stretching, a cross directional stretch is finally carried out again, by transverse pre-tension, the machine-direction oriented of the fiber in material is reduced, and reduces longitudinal stretching difficulty, to reduce PTFE film fento fracture damage in longitudinal forming process, the porosity of PTFE film can effectively improve.The invention also discloses the PTFE microporous barrier using above method preparation and using the compound proton exchange membrane of the PTFE micropore film preparation.
Description
Technical field
The present invention relates to a kind of high performance PTFE microporous barrier and preparation method thereof and use the PTFE microporous barrier made
Standby compound proton exchange membrane, the compound proton exchange membrane can be used as ionic exchange film for fuel cell.
Background technique
Developing low-cost, Proton conducting height, high mechanical strength, chemistry and high-temperature electrochemistry stability are good, ambient humidity shadow
The forward position and impetus that the novel proton exchange membranes low with gas permeability are current fuel cell technology tackling key problem are rung, it is international at present
It has generally used in the market perfluorosulfonic acid proton exchange film (PFSI), in order to further increase performance, related researcher
Available new material is studied, including partially fluorinated, fluorine free polymer dielectric film and it is organic inorganic compounding
Proton exchange membrane, wherein additive includes inorganic ceramics and the sulfonation such as silica, titanium oxide, zirconium oxide, borate, heteropoly acid
A variety of inorganic compounds such as single-walled carbon nanotube.Domestic and international such as company, Du Pont is successively proposed Nafion/PTFE composite membrane, this
Kind composite membrane generally uses the PTFE composite strengthening film of sandwich structure, and thickness is respectively 15~20 μm, can obviously improve proton
The mechanical strength of exchange membrane increases the performances such as service life, but the aperture to PTFE film, porosity, intensity and uniformity are all
More stringent requirements are proposed.
PTFE microporous barrier is tangled by a large amount of microfibres and is connected to form, and hole, the junction of fibre bundle are formed between microfibre
As node is generally distributed in island, and configuration of surface is that have araneose microcellular structure, and PTFE microporous barrier is generally by a step
Biaxial tension is first indulged horizontal drawings two-step stretch is drawn again to be made, and node is larger, PTFE charge bar after rolling, the longitudinal extension of charge bar 5~
20 times, calendering band fento degree of orientation is higher, increases the difficulty of further longitudinal stretching.
Summary of the invention
The purpose of the application, which first consists in, provides a kind of preparation method of PTFE microporous barrier, and PTFE is the letter of polytetrafluoroethylene (PTFE)
Claim, the preparation method successively the following steps are included:
(1) PTFE powder, auxiliary agent oil and surfactant are mixed and stirred for uniformly, are then pressed through curing, striking adobe, pushing
It delays and is prepared into the calendering band containing surfactant；Auxiliary agent oil can be gasoline, aviation kerosine etc..
(2) calendering band is stretched through three steps, obtains PTFE microporous barrier after sintering sizing.
Surfactant therein is at least one of fluorine carbon surfactant or silicon class surfactant, fluorine therein
Carbons surfactant can be fluoroacrylic resin, and silicon class surfactant can be modified Nano organosilicon.
Preferably, on the basis of the quality of PTFE powder, the dosage that auxiliary agent has is 20~40%, the dosage of surfactant
It is 2~6 ‰.
Preferably, the three steps stretching in step (2) specifically includes as follows step by step:
(2.1) transverse pre-tension is carried out to calendering band at a temperature of 150~250 DEG C and completed, transverse pre-tension multiplying power is 2
It~6 times, is then heat-treated at 100~150 DEG C；
(2.2) after completing heat treatment, in 150~280 DEG C of progress longitudinal stretchings, longitudinal stretching multiplying power is 2~15 times；
(2.3) it in 220~300 DEG C of progress cross directional stretch, completes after stretching horizontally, cross directional stretch multiplying power is 5~10 times.
In the method, the step of being stretched using three steps, i.e., first transverse pre-tension, again longitudinal stretching, finally carries out one again
Secondary cross directional stretch reduces the machine-direction oriented of the fiber in material by transverse pre-tension, and reduces longitudinal stretching difficulty,
To reduce PTFE film fento fracture damage in longitudinal forming process, the porosity of PTFE film can effectively improve.Due to adding
Enter surfactant, solvent naphtha can be made more uniformly to be wrapped in the particle surface of PTFE powder, it during stretching, can
Reducing macromolecule cohesive energy keeps fiber more easily stretchable, and after introducing surfactant, improves the surface energy of PTFE film, more
Be conducive to the casting of Nafion resin solution during being prepared as proton exchange membrane conducive to PTFE film.
Preferably, when curing, curing temperature is 45-55 DEG C, and the curing time is 16~24 hours.
Under the limitation of above-mentioned condition, it is ensured that can adequately be infiltrated between each raw material, keep auxiliary agent oil living on surface
The surface of PTFE particle is more uniformly wrapped under the assistance of property agent.
Specifically, after striking adobe, material forms columned green body, then carries out pushing calendering to green body, pushes calendering tool
Body are as follows:
Green body is extruded at 30~50 DEG C by the extrusion band sheet material with a thickness of 200~800 microns using flat die；
Then it will be squeezed out in the case where two pressure rollers act on and be made calendering band with a thickness of 60~200 microns with sheet material calendering, two pressure rollers
Roll surface temperature is 30~50 DEG C.Preferably, formed calendering band during, squeeze out the extrusion compression ratio with sheet material be 30~
100.It can effectively improve the puffed degree of PTFE film.
It is preferred that temperature when sintering sizing is 300 DEG C, can have on the basis of guaranteeing that PTFE film has good strength certain
Toughness.
Secondly, the application also provides a kind of PTFE microporous barrier, above-mentioned any preparation method is used to be prepared,
The PTFE microporous barrier has dotted node and long stapled structure.Preferably, the porosity of=90% of the PTFE microporous barrier, it is average
Aperture is 0.2~1 μm, and elongation at break is 180~200%.
The properties CV value such as the ventilative of the PTFE microporous barrier, thickness, grammes per square metre is respectively less than 10%, can be used as excellent matter
The substrate of proton exchange.
The porosity of PTFE film has been significantly greatly increased under identical thickness in its stippled nodes and long fibre structure, has more
Proton exchange channel, while its high microsteping degree makes mechanical strength have a certain upgrade.
Again, the application also provides a kind of compound proton exchange membrane, and above-mentioned PTFE microporous barrier is used to be prepared, tool
Preparation are as follows: using PTFE microporous barrier as basement membrane, be prepared in basement membrane upper perfluor sulfoacid resin solution；This is compound
Proton exchange membrane is for the proton exchange membrane as fuel cell.
For the compound proton exchange membrane in the proton exchange membrane as fuel cell, water and sky is can be effectively reduced in small-bore
Osmosis of the gas in film, meanwhile, higher porosity and degree of fibrosis provide more channels to the conduction of proton,
Make it have good proton conductivity.
Detailed description of the invention
Fig. 1 is 1000 times of electron microscope of PTFE microporous barrier obtained in embodiment 1.
Fig. 2 is 2000 times of electron microscope of PTFE microporous barrier obtained in embodiment 1.
Specific embodiment
Below with reference to embodiment, invention is further described in detail
Embodiment 1
(1) mixing is aged: on the basis of the quality of PTFE powder, the auxiliary agent for being 26% by mass ratio is oily, mass ratio is 3 ‰
Surfactant is uniformly mixed with polytetrafluoroethylene (PTFE), is placed in 50 DEG C of constant temperature ovens and is cured 20 hours.In the present embodiment, it helps
Agent oil uses gasoline, and surfactant uses fluoroacrylic resin.
Then material striking adobe, the pushing calendering of curing will be completed, specifically: powder is pressed into cylinder under a certain pressure
Green body, green body are put into extruder, and column green body is extruded into the extrusion with a thickness of 300 microns at 50 DEG C by flat die
Band sheet material, squeezing out compression ratio is 40；Then two roll surface temperatures be 40 DEG C pressure roller effect under calendering be made it is micro- with a thickness of 200
The calendering band of rice.
(2) stretch film forming: point three steps stretch film forming, and wherein the first step carries out de-oiling for band is rolled at 160 DEG C, then exist
Transverse pre-tension is carried out at 150 DEG C and is completed, and transverse pre-tension multiplying power is 3 times, is then heat-treated at 150 DEG C, and speed is stretched
For 10m/min, longitudinal stretching is carried out at 200 DEG C, indulging and drawing multiplying power is 8, and finally in 250 DEG C of progress cross directional stretch, stretching ratio is
5, thermal finalization is carried out at last 350 DEG C, obtains microporous teflon membran.
The microporous teflon membran, i.e. PTFE microporous barrier, have dotted node and long stapled structure, and micropore is flat
Equal aperture is 0.6 μm, porosity 90%, and with a thickness of 8 μm, elongation at break 180% is breathed freely, the items such as thickness, grammes per square metre
Energy CV value is 5~8%.
Electron-microscope scanning is carried out to the PTFE microporous barrier, obtains the electron microscope of Fig. 1 and Fig. 2.
PTFE microporous barrier and the fixation that the present embodiment production is cut out with polyester box, first clean it with deionized water,
It is dried at 60 DEG C, is then placed in the organic mixed solution of dehydrated alcohol, acetone, isopropanol that volume ratio is 6:1:1 and impregnates
20min, taking-up are dried.With Nafion lotion (concentration 10wt%), ethyl alcohol, isopropanol and the crassitude of DuPont Corporation
10:20:1:1 high-speed stirred 20min prepares to obtain electrolyte solution ketone (NMP) by volume, then multiple using the tape casting preparation
Film is closed, the electrolyte solution of preparation is cast in into glass substrate and on the PTFE microporous barrier fixed with polyester box, use is infrared
Lamp heating, electrolyte solution curtain coating is filled into PTFE microporous barrier, until solvent volatilizees completely, is put into vacuum oven and is carried out heat
Processing, heats 30min at 80 DEG C of temperature, then takes out after natural cooling, compound proton exchange membrane is made.By composite proton
After exchange membrane is removed from glass plate, between being put into metal platen as protective layer with clean silicon rubber, in pressure 1.5MPa, temperature
Precise hot press hot pressing 90S is used under the conditions of 120 DEG C, composite membrane is taken out after natural cooling, and test obtains proton conductivity and is
0.0986S/cm, with a thickness of 11 μm.
Embodiment 2
(1) mixing is aged: on the basis of the quality of PTFE powder, the auxiliary agent for being 26% by mass ratio is oily, mass ratio is 4 ‰
Surfactant is uniformly mixed with polytetrafluoroethylene (PTFE), is placed in 50 DEG C of constant temperature ovens and is cured 20 hours.In the present embodiment, it helps
Agent oil uses aviation kerosine, and surfactant uses modified Nano organosilicon.
Then material striking adobe, the pushing calendering of curing will be completed, specifically: powder is pressed into cylinder under a certain pressure
Green body, green body are put into extruder, and column green body is extruded into the extrusion with a thickness of 300 microns at 50 DEG C by flat die
Band sheet material, squeezing out compression ratio is 50；Then two roll surface temperatures be 40 DEG C pressure roller effect under calendering be made it is micro- with a thickness of 200
The calendering band of rice.
(2) stretch film forming: point three steps stretch film forming, and wherein the first step carries out de-oiling for band is rolled at 160 DEG C, then exist
Transverse pre-tension is carried out at 150 DEG C and is completed, and transverse pre-tension multiplying power is 3 times, is then heat-treated at 150 DEG C, and speed is stretched
For 10m/min, longitudinal stretching is carried out at 200 DEG C, indulging and drawing multiplying power is 8, and finally in 300 DEG C of progress cross directional stretch, stretching ratio is
5, thermal finalization is carried out at last 350 DEG C, obtains microporous teflon membran.
The microporous teflon membran, i.e. PTFE microporous barrier, have dotted node and long stapled structure, and micropore is flat
Equal aperture is 0.5 μm, porosity 95%, and with a thickness of 6 μm, elongation at break 170% is breathed freely, the items such as thickness, grammes per square metre
Energy CV value is 5~9%.
Nafion/PTFE composite membrane is prepared with the tape casting identical in embodiment 1, test obtains proton conductivity and is
0.1031S/cm, with a thickness of 8 μm.
Claims (10)
1. a kind of preparation method of PTFE microporous barrier, it is characterized in that: successively the following steps are included:
(1) PTFE powder, auxiliary agent oil and surfactant are mixed and stirred for uniformly, then after curing, striking adobe, pushing calendering
It is prepared into the calendering band containing surfactant；
(2) calendering band is stretched through three steps, obtains PTFE microporous barrier after sintering sizing.
2. preparation method according to claim 1, it is characterised in that: on the basis of the quality of PTFE powder, what auxiliary agent had
Dosage is 20~40%, and the dosage of surfactant is 2~6 ‰.
3. preparation method according to claim 1, it is characterised in that: when curing, curing temperature is 45~55 DEG C, when curing
Between be 16~24 hours.
4. preparation method according to claim 1, it is characterised in that: after striking adobe, material forms columned green body, then
Pushing calendering is carried out to green body, pushes calendering specifically:
Green body is extruded at 30~50 DEG C by the extrusion band sheet material with a thickness of 200~800 microns using flat die；Then
It will be squeezed out in the case where two pressure rollers act on and roll the calendering band being made with a thickness of 60~200 microns, the roll surface of two pressure rollers with sheet material
Temperature is 30~50 DEG C.
5. the preparation method according to claim 4, it is characterised in that: during forming calendering band, squeeze out band sheet material
Extrusion compression ratio be 30~100.
6. preparation method according to claim 1, it is characterised in that:
Three steps stretching in step (2) specifically includes as follows step by step:
(2.1) transverse pre-tension is carried out to calendering band at a temperature of 150~250 DEG C and completed, transverse pre-tension multiplying power is 2~6
Times, then it is heat-treated at 100~150 DEG C；
(2.2) after completing heat treatment, in 150~280 DEG C of progress longitudinal stretchings, longitudinal stretching multiplying power is 2~15 times；
(2.3) it in 220~300 DEG C of progress cross directional stretch, completes after stretching horizontally, cross directional stretch multiplying power is 5~10 times.
7. preparation method according to claim 1, it is characterised in that:
Temperature when sintering sizing is 350~400 DEG C.
8. a kind of PTFE microporous barrier, which is characterized in that using preparation method system described in claim 1~7 any claim
Standby to form, which has dotted node and long stapled structure.
9. PTFE microporous barrier according to claim 8, which is characterized in that
The porosity of=90% of the PTFE microporous barrier, average pore size are 0.2~1 μm, and elongation at break is 180~200%.
10. a kind of compound proton exchange membrane, which is characterized in that using PTFE micropore film preparation described in claim 8 or 9
At specifically the preparation method comprises the following steps: being prepared using PTFE microporous barrier as basement membrane in basement membrane upper perfluor sulfoacid resin solution；
The compound proton exchange membrane is for the proton exchange membrane as fuel cell.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112717729A (en) * | 2020-12-28 | 2021-04-30 | 杭州泷泽过滤器材有限公司 | PTFE porous membrane and preparation method and application thereof |
| CN113059822A (en) * | 2021-03-18 | 2021-07-02 | 成都希瑞方晓科技有限公司 | Preparation method of expanded polytetrafluoroethylene with enhanced creep resistance |
| CN113471496A (en) * | 2021-06-29 | 2021-10-01 | 上海化工研究院有限公司 | High-proton conductivity high-strength perfluorosulfonic acid composite proton exchange membrane and preparation method thereof |
| CN113921877A (en) * | 2021-10-08 | 2022-01-11 | 安徽元琛环保科技股份有限公司 | Preparation method of composite proton exchange membrane and prepared composite proton exchange membrane |
| CN114011253A (en) * | 2021-11-17 | 2022-02-08 | 中核同辐（长春）辐射技术有限公司 | PTFE microporous membrane surface modification method and application thereof |
| CN114024091A (en) * | 2021-11-08 | 2022-02-08 | 溧阳月泉电能源有限公司 | Lithium ion secondary battery diaphragm and preparation method thereof |
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| CN111378240B (en) * | 2020-03-27 | 2022-03-25 | 山东森荣新材料股份有限公司 | PTFE nanometer mask film and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112717729A (en) * | 2020-12-28 | 2021-04-30 | 杭州泷泽过滤器材有限公司 | PTFE porous membrane and preparation method and application thereof |
| CN112717729B (en) * | 2020-12-28 | 2023-03-21 | 张春燕 | PTFE porous membrane and preparation method and application thereof |
| CN113059822A (en) * | 2021-03-18 | 2021-07-02 | 成都希瑞方晓科技有限公司 | Preparation method of expanded polytetrafluoroethylene with enhanced creep resistance |
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| CN113921877A (en) * | 2021-10-08 | 2022-01-11 | 安徽元琛环保科技股份有限公司 | Preparation method of composite proton exchange membrane and prepared composite proton exchange membrane |
| CN114024091A (en) * | 2021-11-08 | 2022-02-08 | 溧阳月泉电能源有限公司 | Lithium ion secondary battery diaphragm and preparation method thereof |
| CN114024091B (en) * | 2021-11-08 | 2023-08-08 | 溧阳月泉电能源有限公司 | Lithium ion secondary battery diaphragm and preparation method thereof |
| CN114011253A (en) * | 2021-11-17 | 2022-02-08 | 中核同辐（长春）辐射技术有限公司 | PTFE microporous membrane surface modification method and application thereof |
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