CN109921078A - The preparation method of the static spinning membrane of sulfonated polyether-ether-ketone and graphene oxide - Google Patents
The preparation method of the static spinning membrane of sulfonated polyether-ether-ketone and graphene oxide Download PDFInfo
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- CN109921078A CN109921078A CN201910204147.5A CN201910204147A CN109921078A CN 109921078 A CN109921078 A CN 109921078A CN 201910204147 A CN201910204147 A CN 201910204147A CN 109921078 A CN109921078 A CN 109921078A
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- graphene oxide
- ether
- ketone
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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
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- 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
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Abstract
The present invention relates to the preparation methods of a kind of sulfonated polyether-ether-ketone and the static spinning membrane of graphene oxide, it is made of graphene oxide, sulfonated polyether-ether-ketone, chitosan, zinc acetate, polyvinyl alcohol, epoxychloropropane spinning, membrane stability is good, with good proton conductivity and mechanical performance, proton exchange membrane can be used as applied to lithium ion battery field.
Description
Technical field
The invention belongs to technical field of polymer composite materials, and in particular to a kind of sulfonated polyether-ether-ketone and graphene oxide
Static spinning membrane preparation method.
Background technique
Proton exchange membrane is one of the core component of Proton Exchange Membrane Fuel Cells and direct alcohol fuel cell, effect
It is: (1) separates anode and cathode, fuel and air (oxygen) directly mixing is prevented to chemically react；(2) proton conducting, matter
Electron conductivity is higher, and the internal resistance of film is smaller, and the efficiency of fuel cell is higher；(3) electrical insulator prevents electronics from conducting in film,
Electronics, by outside line road direction cathode flow, it is for people to use to generate foreign current by anode.In general, fuel cell PEM material
It must meet the following requirement: (1) inexpensive；(2) high proton conductivity；(3) good mechanical strength (anti-swelling) and size are steady
It is qualitative；(4) excellent chemical stability and electrochemical stability；(5) very low gas or methanol permeability；(6) and catalyst
Layer matching；(7) it is used for a long time and stablizes.
A kind of macromolecule of the sulfonated polyether-ether-ketone as glassy state has good thermal stability and mechanical strength, gas
Infiltration coefficient it is lower.In gas separation process, usually with the presence of vapor, and most of membrane material water-resistant stability by
Limitation, and sulfonated polyether-ether-ketone has excellent water resistance, can be used as the high-molecular matrix material in hybridized film.
Graphene shows excellent performance in many fields in recent years, and functionalization product graphene oxide has only
Special two-dimensional layered structure, surface oxygen-containing group rich in, such as :-OH ,-COOH ,-C=O etc., specific surface with higher
With certain mechanical strength, the mechanical stability and ion selectivity of film can be improved by the addition of graphene oxide, and
Certain proton channel is provided.
Summary of the invention
The purpose of the present invention is to provide the preparation sides of a kind of sulfonated polyether-ether-ketone and the static spinning membrane of graphene oxide
Method.
The technical solution adopted by the present invention to solve the technical problems is: the electrostatic of sulfonated polyether-ether-ketone and graphene oxide
The preparation method of spinning film, comprising the following steps:
1) take graphene oxide that N is added, in N '-dimethyl formamide, ultrasonic disperse 1-2h obtains finely dispersed concentration and is
The graphene oxide dispersion of 3-8wt%；
2) sulfonated polyether-ether-ketone is added into graphene oxide dispersion, stirring is dissolved sulfonated polyether-ether-ketone, must be mixed
Liquid A；
3) it takes chitosan to be added in the acetum that concentration is 0.5-2wt%, stirs to dissolve, acetic acid is then added
Zinc, magnetic agitation 2-3h obtain mixed liquid B；
4) mixed liquor A is added in mixed liquid B under the conditions of magnetic agitation, polyvinyl alcohol and epoxychloropropane is then added
It is dispersed with stirring uniform spinning solution；
5) spinning solution progress electrostatic spinning is obtained into tunica fibrosa；
6) dry after cleaning tunica fibrosa acetone and deionized water, be put into Muffle furnace, under inert gas protection with 1~
The heating rate of 20 DEG C/min is warming up to 200~300 DEG C, is put into tube furnace after keeping the temperature 1~5h, is warming up to 700~800 DEG C of guarantors
1~3h of temperature, obtains the static spinning membrane of sulfonated polyether-ether-ketone and graphene oxide.
Specifically, the sulfonated polyether-ether-ketone, graphene oxide, chitosan, zinc acetate, epoxychloropropane mass ratio be
10-15:3-5:2-5:1-3:0.5-1.1。
Specifically, the concentration of chitosan-acetic acid solution is 3-7wt% in the step 3).
Specifically, in the step 5) electrostatic spinning condition are as follows: spinning voltage 15-20kV, spinning flow velocity 0.5-1ml/
H, receiving distance is 15-20cm.
The invention has the following advantages: static spinning membrane of the invention is by graphene oxide, sulfonated polyether-ether-ketone, shell
Glycan, zinc acetate, polyvinyl alcohol, epoxychloropropane spinning are made, and membrane stability is good, have good proton conductivity and machinery
Performance can be used as proton exchange membrane applied to lithium ion battery field.
Specific embodiment
The following is specific embodiments of the present invention, is described further to technical solution of the present invention, but of the invention
Protection scope is not limited to these examples.It is all to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute
Protection scope within.
Embodiment 1
The preparation method of the static spinning membrane of sulfonated polyether-ether-ketone and graphene oxide, comprising the following steps:
1) take graphene oxide that N is added, in N '-dimethyl formamide, ultrasonic disperse 2h obtains finely dispersed concentration and is
The graphene oxide dispersion of 7wt%；
2) sulfonated polyether-ether-ketone is added into graphene oxide dispersion, stirring is dissolved sulfonated polyether-ether-ketone, must be mixed
Liquid A；
3) take chitosan be added concentration be 1wt% acetum in, stir to dissolve, concentration 6wt%, then plus
Enter zinc acetate, magnetic agitation 3h obtains mixed liquid B；
4) mixed liquor A is added in mixed liquid B under the conditions of magnetic agitation, polyvinyl alcohol and epoxychloropropane is then added
It is dispersed with stirring uniform spinning solution；
5) spinning solution progress electrostatic spinning is obtained into tunica fibrosa, the condition of electrostatic spinning are as follows: spinning voltage 15-20kV, spinning
Flow velocity 0.5-1ml/h, receiving distance is 15-20cm；
6) dry after cleaning tunica fibrosa acetone and deionized water, it is put into Muffle furnace, under inert gas protection with 15
DEG C/heating rate of min is warming up to 300 DEG C, it is put into tube furnace after protecting 2h, is warming up to 730 DEG C of heat preservation 2h, obtains sulfonated polyether ether
The static spinning membrane of ketone and graphene oxide.
The sulfonated polyether-ether-ketone, graphene oxide, chitosan, zinc acetate, epoxychloropropane mass ratio be 12:5:3:
1:0.7。
Embodiment 2
The preparation method of the static spinning membrane of sulfonated polyether-ether-ketone and graphene oxide, comprising the following steps:
1) take graphene oxide that N is added, in N '-dimethyl formamide, ultrasonic disperse 1h obtains finely dispersed concentration and is
The graphene oxide dispersion of 3wt%；
2) sulfonated polyether-ether-ketone is added into graphene oxide dispersion, stirring is dissolved sulfonated polyether-ether-ketone, must be mixed
Liquid A；
3) it takes chitosan to be added in the acetum that concentration is 1.5wt%, stirs to dissolve, concentration 3wt%, then
Zinc acetate is added, magnetic agitation 2h obtains mixed liquid B；
4) mixed liquor A is added in mixed liquid B under the conditions of magnetic agitation, polyvinyl alcohol and epoxychloropropane is then added
It is dispersed with stirring uniform spinning solution；
5) spinning solution progress electrostatic spinning is obtained into tunica fibrosa, the condition of electrostatic spinning are as follows: spinning voltage 15-20kV, spinning
Flow velocity 0.5-1ml/h, receiving distance is 15-20cm；
6) dry after cleaning tunica fibrosa acetone and deionized water, it is put into Muffle furnace, under inert gas protection with 20
DEG C/heating rate of min is warming up to 250 DEG C, it is put into tube furnace after keeping the temperature 3h, is warming up to 800 DEG C of heat preservation 1h, obtains sulfonated polyether
The static spinning membrane of ether ketone and graphene oxide.
The sulfonated polyether-ether-ketone, graphene oxide, chitosan, zinc acetate, epoxychloropropane mass ratio be 10:3:2:
2:1.1。
Embodiment 3
The preparation method of the static spinning membrane of sulfonated polyether-ether-ketone and graphene oxide, comprising the following steps:
1) take graphene oxide that N is added, in N '-dimethyl formamide, ultrasonic disperse 1.5h obtains finely dispersed concentration and is
The graphene oxide dispersion of 8wt%；
2) sulfonated polyether-ether-ketone is added into graphene oxide dispersion, stirring is dissolved sulfonated polyether-ether-ketone, must be mixed
Liquid A；
3) it takes chitosan to be added in the acetum that concentration is 0.5wt%, stirs to dissolve, concentration 5wt%, then
Zinc acetate is added, magnetic agitation 2h obtains mixed liquid B；
4) mixed liquor A is added in mixed liquid B under the conditions of magnetic agitation, polyvinyl alcohol and epoxychloropropane is then added
It is dispersed with stirring uniform spinning solution；
5) spinning solution progress electrostatic spinning is obtained into tunica fibrosa, the condition of electrostatic spinning are as follows: spinning voltage 15-20kV, spinning
Flow velocity 0.5-1ml/h, receiving distance is 15-20cm；
6) dry after cleaning tunica fibrosa acetone and deionized water, it is put into Muffle furnace, under inert gas protection with 1
DEG C/heating rate of min is warming up to 200 DEG C, it is put into tube furnace after keeping the temperature 1h, is warming up to 700 DEG C of heat preservation 3h, obtains sulfonated polyether
The static spinning membrane of ether ketone and graphene oxide.
The sulfonated polyether-ether-ketone, graphene oxide, chitosan, zinc acetate, epoxychloropropane mass ratio be 15:4:5:
3:0.5。
Embodiment 4
The preparation method of the static spinning membrane of sulfonated polyether-ether-ketone and graphene oxide, comprising the following steps:
1) take graphene oxide that N is added, in N '-dimethyl formamide, ultrasonic disperse 2h obtains finely dispersed concentration and is
The graphene oxide dispersion of 5wt%；
2) sulfonated polyether-ether-ketone is added into graphene oxide dispersion, stirring is dissolved sulfonated polyether-ether-ketone, must be mixed
Liquid A；
3) take chitosan be added concentration be 2wt% acetum in, stir to dissolve, concentration 7wt%, then plus
Enter zinc acetate, magnetic agitation 3h obtains mixed liquid B；
4) mixed liquor A is added in mixed liquid B under the conditions of magnetic agitation, polyvinyl alcohol and epoxychloropropane is then added
It is dispersed with stirring uniform spinning solution；
5) spinning solution progress electrostatic spinning is obtained into tunica fibrosa, the condition of electrostatic spinning are as follows: spinning voltage 15-20kV, spinning
Flow velocity 0.5-1ml/h, receiving distance is 15-20cm；
6) dry after cleaning tunica fibrosa acetone and deionized water, it is put into Muffle furnace, under inert gas protection with 8
DEG C/heating rate of min is warming up to 220 DEG C, it is put into tube furnace after keeping the temperature 5h, is warming up to 770 DEG C of heat preservation 2.5h, obtained sulfonation and gather
The static spinning membrane of ether ether ketone and graphene oxide.
The sulfonated polyether-ether-ketone, graphene oxide, chitosan, zinc acetate, epoxychloropropane mass ratio be 13:4:4:
2:0.9。
Claims (4)
1. the preparation method of the static spinning membrane of sulfonated polyether-ether-ketone and graphene oxide, which comprises the following steps:
1) take graphene oxide that N is added, in N '-dimethyl formamide, it is 3- that ultrasonic disperse 1-2h, which obtains finely dispersed concentration,
The graphene oxide dispersion of 8wt%；
2) sulfonated polyether-ether-ketone is added into graphene oxide dispersion, stirring dissolves sulfonated polyether-ether-ketone, obtains mixed liquor A；
3) it takes chitosan to be added in the acetum that concentration is 0.5-2wt%, stirs to dissolve, zinc acetate, magnetic is then added
Power stirring 2-3h obtains mixed liquid B；
4) mixed liquor A is added in mixed liquid B under the conditions of magnetic agitation, polyvinyl alcohol and epoxychloropropane stirring is then added
Be uniformly dispersed to obtain spinning solution；
5) spinning solution progress electrostatic spinning is obtained into tunica fibrosa；
6) dry after cleaning tunica fibrosa acetone and deionized water, it is put into Muffle furnace, under inert gas protection with 1~20
DEG C/heating rate of min is warming up to 200~300 DEG C, it is put into tube furnace after keeping the temperature 1~5h, is warming up to 700~800 DEG C of heat preservations
1~3h obtains the static spinning membrane of sulfonated polyether-ether-ketone and graphene oxide.
2. the preparation method of the static spinning membrane of sulfonated polyether-ether-ketone as described in claim 1 and graphene oxide, feature
Be, the sulfonated polyether-ether-ketone, graphene oxide, chitosan, zinc acetate, epoxychloropropane mass ratio be 10-15:3-5:
2-5:1-3:0.5-1.1。
3. the preparation method of the static spinning membrane of sulfonated polyether-ether-ketone as described in claim 1 and graphene oxide, feature
It is, the concentration of chitosan-acetic acid solution is 3-7wt% in the step 3).
4. the preparation method of the static spinning membrane of sulfonated polyether-ether-ketone as described in claim 1 and graphene oxide, feature
It is, the condition of electrostatic spinning in the step 5) are as follows: spinning voltage 15-20kV, spinning flow velocity 0.5-1ml/h receive distance
For 15-20cm.
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Citations (4)
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|---|---|---|---|---|
| CN102827386A (en) * | 2012-08-21 | 2012-12-19 | 江苏大学 | Preparation method of polyether-ether-ketone/graphene oxide nano-composite film |
| CN104069752A (en) * | 2014-06-27 | 2014-10-01 | 天津大学 | Sulfonated polyether-ether-ketone-amino acid modified graphene oxide hybrid membrane and preparation and application thereof |
| CN107946619A (en) * | 2017-11-09 | 2018-04-20 | 北京秦天科技集团有限公司 | The copolymer material and its proton exchange membrane preparation method of high sulfonated polyether-ether-ketone and graphene oxide |
| CN108998892A (en) * | 2017-06-07 | 2018-12-14 | 南京理工大学 | A kind of preparation method of chitosan-graphene oxide/polyacrylonitrile double-layer nanometer tunica fibrosa |
-
2019
- 2019-03-18 CN CN201910204147.5A patent/CN109921078A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827386A (en) * | 2012-08-21 | 2012-12-19 | 江苏大学 | Preparation method of polyether-ether-ketone/graphene oxide nano-composite film |
| CN104069752A (en) * | 2014-06-27 | 2014-10-01 | 天津大学 | Sulfonated polyether-ether-ketone-amino acid modified graphene oxide hybrid membrane and preparation and application thereof |
| CN108998892A (en) * | 2017-06-07 | 2018-12-14 | 南京理工大学 | A kind of preparation method of chitosan-graphene oxide/polyacrylonitrile double-layer nanometer tunica fibrosa |
| CN107946619A (en) * | 2017-11-09 | 2018-04-20 | 北京秦天科技集团有限公司 | The copolymer material and its proton exchange membrane preparation method of high sulfonated polyether-ether-ketone and graphene oxide |
Non-Patent Citations (1)
| Title |
|---|
| REYES-RODRIGUEZ J L , ESCORIHUELA J , A GARCÍA-BERNABÉ, ET AL.: "Proton conducting electrospun sulfonated polyether ether ketone graphene oxide composite membranes", 《RSC ADVANCES》 * |
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