CN104448771A - P-aminobenzene sulfonic acid graphene oxide grafted sulfonated polyetheretherketone proton exchange membrane material and preparation method thereof - Google Patents
P-aminobenzene sulfonic acid graphene oxide grafted sulfonated polyetheretherketone proton exchange membrane material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a p-aminobenzene sulfonic acid graphene oxide grafted sulfonated polyetheretherketone proton exchange membrane material. The proton exchange membrane material is characterized by being formed by penetrating p-aminobenzene sulfonic acid graphene oxide grafted-modified sulfonated polyetheretherketone serving as straight chains through epoxy resin cross-linked networks as a main body, wherein the mass ratio of epoxy resin to p-aminobenzene sulfonic acid graphene oxide grafted-modified sulfonated polyetheretherketone is (0.2-1.5): 1. The epoxy resin semi-interpenetrating network p-aminobenzene sulfonic acid graphene oxide grafted sulfonated polyetheretherketone proton exchange membrane material disclosed by the invention has the characteristics of low preparation cost, high electrical conductivity, good methanol diffusion resistance and good heat resistance. At 20 DEG C-90 DEG C, the electrical conductivity is 2.90*10<-3>-5.30*10<-1>S.cm<-1>, methanol-diffusion-resistant coefficient reaches 2.00*10<-7>- 9.00*10<-7>cm<2>.s<-1> and the water absorption rate is 12-100%.
Description
Technical field
The present invention relates to epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material and preparation method thereof.
Background technology
To advance today that Green Development, cycle development, low carbon development are main task, improve efficiency of energy utilization, exploitation clean energy has become the inexorable trend of scientific research.Fuel cell (DMFC) with its environmental protection, the feature such as energy-conservation, efficient, easy to use, by development and application at numerous areas.
In fuel cell, proton exchange membrane is as the core parts of MEA, and in the selection using material, mainly from leading proton performance, chemical stability, research is set about in the aspects such as mechanical property.Late 1960s, first polystyrene sulfonate film is used in PEMFC, but there are some fatal defects as proton exchange membrane in styrene sulfonic acid material, it is in use easily degraded, not only cause the shortening of battery life, power density low, but also pollute the generation water of battery, cosmonaut cannot be used.Along with the continuous progress of science and technology, the continuous renewal of fuel cell technology, the development of Proton Exchange Membrane Fuel Cells is actually the test to proton exchange membrane weather resistance.So far, the most frequently used proton exchange membrane (PEMFC) is still Du Pont company in 1962 and produces novel perfluoro sulfonic acid membrane proton exchange membrane (Nafion), Nafion film solves some defects of styrene sulfonic acid proton exchange membrane preferably, and it makes the life-span of fuel cell greatly improve.But fuel cell technology research and development many decades, fail to promote on a large scale, except the problem such as existence and stability, weather resistance, make a thorough investigation, sky high cost is also business-like bottleneck always.Active development novel material is the only way which must be passed solving this several large problem, is also the focus of current Proton Exchange Membrane Fuel Cells research.
Sulfonated reagent is adopted to carry out sulfonation to PEEK, sulfonic acid group is incorporated on PEEK main chain, due to sulfonic group aqueous favoring and the existence of the hydrophobic phase of phenyl ring, ehter bond etc. on polymer backbone, make material have certain proton conductivity, and the alcohol-rejecting ability of higher physical strength, resistance toheat and the excellence of SPEEK material can meet the requirement of fuel cell to proton exchange membrane material.But the SPEEK film proton conductivity of highly sulfonated (DS > 90%) is higher, simultaneously thoroughly alcohol coefficient and water swelling ratio all higher, even lost efficacy because of excessively swelling; And the SPEEK film of low sulfonation degree (DS < 40%) hinders alcohol and water resistant swelling behavior is all excellent, but proton conductivity is lower, far away from Nafion film.Therefore, on the conceptual design to SPEEK proton exchange membrane modifying, in the urgent need to considering SPEEK sulfonation degree and modification mode, develop that a kind of cost is low, proton conductivity is high, the novel proton exchange membranes of features good methanol diffusion resistance.
Summary of the invention
An object of the present invention is to provide epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material.
Two of object of the present invention is the preparation method providing this proton exchange membrane material.
For achieving the above object, reaction mechanism of the present invention is:
For achieving the above object, the present invention adopts following technical scheme:
A kind of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material, it is characterized in that this proton exchange membrane material is based on cross linking of epoxy resin network, the sulfonated polyether-ether-ketone of Sulphanilic Acid graphene oxide graft modification runs through as straight chain and is formed in above-mentioned cross-linked network, and the mass ratio of the sulfonated polyether-ether-ketone of its epoxy resin and the graft modification of Sulphanilic Acid graphene oxide is: (0.2 ~ 1.5): 1; The structural formula of described Sulphanilic Acid graphene oxide graft sulfonation polyether-ether-ketone is as follows:
Wherein m=1 ~ 5, n=10 ~ 50; The square of black represents graphene oxide.
Prepare a method for above-mentioned epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material, it is characterized in that the concrete steps of the method are:
A. by sulfonation degree be 50 ~ 90% sulfonated polyether-ether-ketone dissolve in a solvent, be mixed with the solution that mass percent concentration is 2.0% ~ 20.0%; Add NaBH again
4pressed powder, at 90 ~ 130 DEG C, inert atmosphere protection, stirring reaction 12 ~ 15 hours, gets supernatant liquor; Wherein sulfonated polyether-ether-ketone and NaBH
4equivalence ratio is 1: (1.0 ~ 5.0);
B. graphene oxide and coupling agent are joined in toluene, at 80 ~ 100 DEG C, protection of inert gas, mechanical stirring 12 ~ 24 hours, wherein the equivalence ratio of graphene oxide, coupling agent and toluene is: 1:(20 ~ 60): (70 ~ 90);
C. the solution that step b obtains is joined in step a gained supernatant liquid, at 0 ~ 7 DEG C, ultrasonic reaction 18 ~ 28 hours, wherein the equivalence ratio of sulfonated polyether-ether-ketone and graphene oxide is 1: (0.03 ~ 0.20);
D. Sulphanilic Acid is joined in the solution of step c gained, inert atmosphere protection, at 50 ~ 60 DEG C, stirring reaction 20 ~ 45 hours; Wherein the equivalence ratio of sulfonated polyether-ether-ketone and Sulphanilic Acid is 1: (0.15 ~ 0.85);
E. after epoxy resin being heated to 50 DEG C, being added in step e gained solution, more dropwise adding diethylenetriamine, inert atmosphere protection, stirring reaction 0.5 ~ 1 hour at 120 ~ 160 DEG C, preparation liquid; Wherein the equivalence ratio of sulfonated polyether-ether-ketone and epoxy resin is 1:(0.10 ~ 0.40); The equivalence ratio of epoxy resin and diethylenetriamine is 1:(0.01 ~ 0.02);
F. the film making solution of step e gained is cooled to room temperature, centrifugal disgorging, get supernatant liquor casting film-forming on glass panels, and in baking oven at 60 ~ 120 DEG C dry 10 ~ 24 hours, remove solvent, obtain epoxy resin Semi-IPN Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material.。
Proton exchange membrane material of the present invention adopts sulfonated polyether-ether-ketone compared with highly sulfonated as body material, auxiliary by cross linking of epoxy resin reaction, too high with the water-intake rate overcoming highly sulfonated SPEEK existence, the shortcoming of composite membrane less stable, and ensure that composite membrane has certain physical strength and good alcohol-rejecting ability.What the introducing of the graphene oxide of silane coupling agent modified improve sulfonated polyether-ether-ketone mould material leads proton performance; A large amount of sulfonic acid group is by the introducing of chemical bond mode, the proton conductivity of further raising proton exchange membrane, avoid the physics of sulfonic acid group to run off, improve the work-ing life of film, epoxy resin semi-intercrossing network increases proton exchange membrane dimensional stability and water resistant swelling behavior.
Epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material prepared by the present invention has that preparation cost is low, specific conductivity is high, the feature of features good methanol diffusion resistance and good heat resistance.Specific conductivity at 20 DEG C ~ 90 DEG C is 2.90 × 10
-3~ 5.30 × 10
-1scm
-1, resistance alcohol coefficient reaches 2.00 × 10
-7~ 9.00 × 10
-7cm
2s
-1, water-intake rate is 12 ~ 100%.
Accompanying drawing explanation
Fig. 1 is the structural representation of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyether-ether-ketone of the present invention.
Fig. 2 is the infrared spectrum of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyether-ether-ketone prepared by the present invention.
Fig. 3 is the hot weightless picture of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyether-ether-ketone prepared by the present invention.
Fig. 4 is the SEM figure of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyether-ether-ketone prepared by the present invention.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
(1) in the 100 mL there-necked flasks that magnet rotor stirring, prolong, thermometer are housed, be 65% by the SPEEK(sulfonation degree of (1.7000g, 0.0050mol)) be dissolved in the DMAc solvent of 30 mL, open magnetic agitation, oil bath pan is heated to 60 DEG C, is made into film making solution;
(2) under nitrogen protection, the disposable NaBH adding (0.1892g, 0.0050mol) in the film making solution of step (1) gained
4, be warming up to 100 DEG C of back flow reaction 12 hours, centrifugal purification, obtains supernatant liquid;
(3) graphene oxide (0.08825g) and coupling agent (3.10g, 1.5ml) are joined in toluene (7g, 8ml), at 100 DEG C, protection of inert gas, mechanical stirring 12 hours.
(4) in the 500mL there-necked flask that magnet rotor stirring, prolong, HCl absorption unit are housed, by (3) solution in DMAc solvent, the supernatant liquid of step (2) gained is dropwise dripped, stirring reaction 24 hours under ice-water bath.
(5) in the 500mL there-necked flask that magnet rotor stirring, prolong, HCl absorption unit are housed; under nitrogen protection; by (0.4330g; Sulphanilic Acid 0.0025mol) joins in the film making solution of step (4) gained; at 60 DEG C, stirring reaction 48 hours.
(6) (0.39848g, 0.001mol) epoxy resin is dissolved in DMAc solvent, adds (0.04656ml) diethylenetriamine, stirring reaction 30min at 150 DEG C.
(7) film making solution of step (6) gained is cooled to room temperature, centrifugal throw out of going out, get 10 mL supernatant liquids casting film-forming on glass panels, obtain wet film, first at 60 DEG C dry 8 hours, then at 80 DEG C dry 4 hours, take out from baking oven, naturally cool to after room temperature until it, take off film, obtain epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material.
To the epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film application experiment obtained by above-described embodiment, its process and result as described below:
(1) epoxy resin semi-intercrossing network phosphonitrile graft modification SPEEK proton exchange membrane conductivity test:
Adopt and exchange two-probe method on the homemade device in laboratory, respectively analog D MFC anode acidic medium and negative electrode water medium, the proton conductivity of test membrane sample.Detected temperatures is 25 ~ 90 DEG C.According to Ampere's law, calculate the specific conductivity of film sample:
lthe thickness (cm) of film sample
auseful area (the cm of film sample
2)
rthe real impedance (Ω) of film sample
Proton conductivity (the Scm of σ film sample
-1)
By test, specific conductivity when obtaining epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film 30 DEG C is 5.00 × 10
-3scm
-1, when 80 DEG C, reach maximum value 4.2 × 10
-2scm
-1.
(2) epoxy resin Semi-IPN net Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film alcohol-rejecting ability test:
Adopt the alcohol-rejecting ability of homemade barrier film diffusion cell evaluated for film.A simple and easy communicating vessel device, proton exchange membrane separates two and half Room, and 50 mL concentration 5.00 molL are injected in left half Room
-1methanol solution, the deionized water of same volume is injected in right half Room, and two halves indoor are put into magnetic stir bar and stirred, and guarantee that in test process, strength of solution is even.Adopt methanol concentration situation over time in gas chromatographic measurement deionized water.Spread second law by Fick and can obtain methanol permeability:
pmethanol permeability (the cm of film sample
2s
-1)
sdeionized water side methanol concentration velocity of variation (molL in time
-1s
-1)
v 2 deionized water Side Volume (mL)
lthe thickness (cm) of film sample
auseful area (the cm of film sample
2)
c 10 initial methanol concentration (the molL of methanol solution side
-1)
By test, under reaction conditions described above, the resistance alcohol coefficient of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film is 2.11 × 10
-7cm
2s
-1.
(3) epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film water-intake rate test:
Film sample length and width being about 20 × 10 mm is placed in baking oven, and dry 24 h at 120 DEG C, claim to obtain dry film quality
m dry , then film is immersed in deionized water, after at room temperature soaking 24 h, takes out wet film, suck surperficial moisture content with filter paper, claim to obtain wet film quality
m wet .Sample repeated test is averaged for three times.The water-intake rate S of film
wfor:
By test, under such as above-mentioned reaction conditions, the water-intake rate of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film is 12.3%.
Embodiment 2:
(1) in the 100 mL there-necked flasks that magnet rotor stirring, prolong, thermometer are housed, be 75 by the SPEEK(sulfonation degree of (3.4000g, 0.0100mol)) be dissolved in the DMAc solvent of 30 mL, open magnetic agitation, oil bath pan is heated to 100 DEG C, is made into film making solution;
(2) under nitrogen protection, the disposable NaBH4 adding (0.3783g, 0.0100mol) in the film making solution of step (1) gained, be warming up to 90 DEG C of back flow reaction 18 hours, centrifugal purification, obtains supernatant liquid;
(3) graphene oxide (0.1765g) and coupling agent (6.20g, 0.31ml) are joined in toluene (14g, 16ml), at 100 DEG C, protection of inert gas, mechanical stirring 12 hours.
(4) in the 500mL there-necked flask that magnet rotor stirring, prolong, HCl absorption unit are housed, by (3) solution in DMAc solvent, the supernatant liquid of step (2) gained is dropwise dripped, stirring reaction 24 hours under ice-water bath.
(5) in the 500mL there-necked flask that magnet rotor stirring, prolong, HCl absorption unit are housed; under nitrogen protection, the Sulphanilic Acid of (0.8660g, 0.005mol) is joined in the film making solution of step (4) gained; at 60 DEG C, stirring reaction 48 hours.
(6) (0.39848g, 0.001mol) epoxy resin is dissolved in DMAc solvent, adds (0.04656ml) diethylenetriamine, stirring reaction 30min at 150 DEG C.
(7) film making solution of step (6) gained is cooled to room temperature, centrifugal throw out of going out, get 10 mL supernatant liquids casting film-forming on glass panels, obtain wet film, first at 60 DEG C dry 8 hours, then at 80 DEG C dry 4 hours, take out from baking oven, naturally cool to after room temperature until it, take off film, obtain epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material.
To the epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film application experiment obtained by above-described embodiment, its process and result as described below:
(1) epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film specific conductivity test:
Testing method as described in Example 1.Specific conductivity during epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film 30 DEG C is 7.98 × 10
-2scm
-1, when 84 DEG C, reach maximum value 4.50 × 10
-2scm
-1.
(2) epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film alcohol-rejecting ability test:
Testing method as described in Example 1.The resistance alcohol coefficient of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film is 9.47 × 10
-7cm
2s
-1.
(3) epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film water-intake rate test:
Testing method as described in Example 1.The water-intake rate of poly-(Sulphanilic Acid graphene oxide-ether ether ketone) proton exchange membrane of epoxy resin semi-intercrossing network sulfonation is 18.8%.
Embodiment 3:
(1) in the 100 mL there-necked flasks that magnet rotor stirring, prolong, thermometer are housed, SPEEK(sulfonation degree 68% by (2.0400g, 0.0060mol)) be dissolved in the DMAc solvent of 30 mL, open magnetic agitation, oil bath pan is heated to 100 DEG C, is made into film making solution;
(2) under nitrogen protection, the disposable NaBH4 adding (0.2270g, 0.0060mol) in the film making solution of step (1) gained, be warming up to 120 DEG C of back flow reaction 10 hours, centrifugal purification, obtains supernatant liquid;
(3) graphene oxide (0.26475g) and coupling agent (9.3g, 9ml) are joined in toluene (21g, 24ml), at 100 DEG C, protection of inert gas, mechanical stirring 12 hours.
(4) in the 500mL there-necked flask that magnet rotor stirring, prolong, HCl absorption unit are housed, by (3) solution in DMAc solvent, the supernatant liquid of step (2) gained is dropwise dripped, stirring reaction 24 hours under ice-water bath.
(5) in the 500mL there-necked flask that magnet rotor stirring, prolong, HCl absorption unit are housed; under nitrogen protection; by (1.2990g; Sulphanilic Acid 0.0075mol) joins in the film making solution of step (4) gained; at 60 DEG C, stirring reaction 48 hours.
(6) (0.79696g, 0.002mol) epoxy resin is dissolved in DMAc solvent, adds (0.09312ml) diethylenetriamine, stirring reaction 30min at 150 DEG C.
(7) film making solution of step (6) gained is cooled to room temperature, centrifugal throw out of going out, get 10 mL supernatant liquids casting film-forming on glass panels, obtain wet film, first at 60 DEG C dry 8 hours, then at 80 DEG C dry 4 hours, take out from baking oven, naturally cool to after room temperature until it, take off film, obtain epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material.
To the epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film application experiment obtained by above-described embodiment, its process and result as described below:
(1) epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film specific conductivity test:
Testing method as described in Example 1.Specific conductivity during epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film 30 DEG C is 8.24 × 10
-3scm
-1, when 70 DEG C, reach maximum value 6.20 × 10
-2scm
-1.
(2) epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film alcohol-rejecting ability test:
Testing method as described in Example 1.The resistance alcohol coefficient of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film is 8.79 × 10
-7cm
2s
-1.
(3) epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film water-intake rate test:
Testing method as described in Example 1.The water-intake rate of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film is 11.3%.
The structural representation of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material of the present invention.By FTIR, thermal characteristics, the performance of the means such as SEM to synthetic product characterizes, and test result is see Fig. 2, Fig. 3 and Fig. 4.
Fig. 2 characterizing epoxy resin is successfully cross-linked, and sulfoxidation graphite rare grafting SPEEK structure exists.Fig. 3 shows that the mould material of epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyether-ether-ketone has excellent thermal stability, Fig. 4 finds out after cross linking of epoxy resin process, epoxy resin forms external phase region, and in the middle of being run through by SPEEK, can be observed the separating interface of two kinds of polymkeric substance and not obvious, surrounded by epoxy resin around SPEEK particle, illustrate that formation runs through network structure.
Claims (2)
1. an epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material, it is characterized in that this proton exchange membrane material is based on cross linking of epoxy resin network, the sulfonated polyether-ether-ketone of Sulphanilic Acid graphene oxide graft modification runs through as straight chain and is formed in above-mentioned cross-linked network, and the mass ratio of the sulfonated polyether-ether-ketone of its epoxy resin and the graft modification of Sulphanilic Acid graphene oxide is: (0.2 ~ 1.5): 1; The structural formula of described Sulphanilic Acid graphene oxide graft sulfonation polyether-ether-ketone is as follows:
Wherein m=1 ~ 5, n=10 ~ 50; The square of black represents graphene oxide.
2. prepare a method for epoxy resin semi-intercrossing network Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material according to claim 1, it is characterized in that the concrete steps of the method are:
A. by sulfonation degree be 50 ~ 90% sulfonated polyether-ether-ketone dissolve in a solvent, be mixed with the solution that mass percent concentration is 2.0% ~ 20.0%; Add NaBH again
4pressed powder, at 90 ~ 130 DEG C, inert atmosphere protection, stirring reaction 12 ~ 15 hours, gets supernatant liquor; Wherein sulfonated polyether-ether-ketone and NaBH
4equivalence ratio is 1: (1.0 ~ 5.0);
B. graphene oxide and coupling agent are joined in toluene, at 80 ~ 100 DEG C, protection of inert gas, mechanical stirring 12 ~ 24 hours, wherein the equivalence ratio of graphene oxide, coupling agent and toluene is: 1:(20 ~ 60): (70 ~ 90);
C. the solution that step b obtains is joined in step a gained supernatant liquid, at 0 ~ 7 DEG C, ultrasonic reaction 18 ~ 28 hours, wherein the equivalence ratio of sulfonated polyether-ether-ketone and graphene oxide is 1: (0.03 ~ 0.20);
D. Sulphanilic Acid is joined in the solution of step c gained, inert atmosphere protection, at 50 ~ 60 DEG C, stirring reaction 20 ~ 45 hours; Wherein the equivalence ratio of sulfonated polyether-ether-ketone and Sulphanilic Acid is 1: (0.15 ~ 0.85);
E. after epoxy resin being heated to 50 DEG C, being added in step e gained solution, more dropwise adding diethylenetriamine, inert atmosphere protection, stirring reaction 0.5 ~ 1 hour at 120 ~ 160 DEG C, preparation liquid; Wherein the equivalence ratio of sulfonated polyether-ether-ketone and epoxy resin is 1:(0.10 ~ 0.40); The equivalence ratio of epoxy resin and diethylenetriamine is 1:(0.01 ~ 0.02);
F. the film making solution of step e gained is cooled to room temperature, centrifugal disgorging, get supernatant liquor casting film-forming on glass panels, and in baking oven at 60 ~ 120 DEG C dry 10 ~ 24 hours, remove solvent, obtain epoxy resin Semi-IPN Sulphanilic Acid graphene oxide graft sulfonation polyetheretherketoneproton proton exchange film material.
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| CN104852065A (en) * | 2015-05-26 | 2015-08-19 | 宁波工程学院 | Composite proton exchange membrane for direct methanol fuel cell, and preparation method of composite proton exchange membrane |
| CN104893240A (en) * | 2015-06-17 | 2015-09-09 | 上海大学 | SPEEK (sulfonated poly (ether ether ketone)) proton exchange membrane material with epoxy resin interpenetrating polymer network and preparation method of SPEEK proton exchange membrane material |
| CN104893275A (en) * | 2015-06-17 | 2015-09-09 | 上海大学 | Proton exchange membrane material with semi-interpenetrating network formed by p-aminobenzene sulfonic acid graphene oxide doped SPEEK (sulfonated poly (ether ether ketone))/epoxy resin and preparation method of proton exchange membrane material |
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| CN101225181B (en) * | 2007-12-06 | 2011-05-04 | 上海大学 | Y2O3 modified sulfonated polyetheretherketone proton exchange membrane and preparation method thereof |
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| CN101867050A (en) * | 2010-06-08 | 2010-10-20 | 南通大学 | Composite proton exchange membrane |
| CN102838863B (en) * | 2012-09-18 | 2014-12-31 | 成都博立恒科技有限公司 | Novel polymer proton exchange membrane and preparation method thereof |
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| CN104852065A (en) * | 2015-05-26 | 2015-08-19 | 宁波工程学院 | Composite proton exchange membrane for direct methanol fuel cell, and preparation method of composite proton exchange membrane |
| CN104852065B (en) * | 2015-05-26 | 2017-06-30 | 宁波工程学院 | A kind of compound proton exchange membrane for DMFC and preparation method thereof |
| CN104893240A (en) * | 2015-06-17 | 2015-09-09 | 上海大学 | SPEEK (sulfonated poly (ether ether ketone)) proton exchange membrane material with epoxy resin interpenetrating polymer network and preparation method of SPEEK proton exchange membrane material |
| CN104893275A (en) * | 2015-06-17 | 2015-09-09 | 上海大学 | Proton exchange membrane material with semi-interpenetrating network formed by p-aminobenzene sulfonic acid graphene oxide doped SPEEK (sulfonated poly (ether ether ketone))/epoxy resin and preparation method of proton exchange membrane material |
| CN106633626A (en) * | 2016-09-27 | 2017-05-10 | 广东银禧科技股份有限公司 | Graphene/polyetheretherketone composite powder material for SLS (Selective Laser Sintering) and preparation method |
| CN106633626B (en) * | 2016-09-27 | 2019-03-22 | 广东银禧科技股份有限公司 | Graphene/polyether-ether-ketone composite powder material and preparation method for SLS |
| CN107963969A (en) * | 2016-10-19 | 2018-04-27 | 株式会社半导体能源研究所 | Graphite ene compound and its manufacture method, electrolyte, electrical storage device |
| US11495826B2 (en) | 2016-10-19 | 2022-11-08 | Semiconductor Energy Laboratory Co., Ltd. | Graphene compound and manufacturing method thereof, electrolyte, and power storage device |
| CN111342094A (en) * | 2020-04-02 | 2020-06-26 | 陈婧 | Preparation method of rare earth doped perfluorosulfonic acid membrane |
| CN113072853A (en) * | 2021-03-04 | 2021-07-06 | 杭州世子合德生物科技有限公司 | Corrosion-resistant coating material and preparation method thereof |
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