CN109411796A - A kind of crosslinking proton exchange membrane and preparation method for vanadium cell - Google Patents
A kind of crosslinking proton exchange membrane and preparation method for vanadium cell Download PDFInfo
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Abstract
The present invention provides a kind of crosslinking proton exchange membranes and preparation method for vanadium cell.This method first passes through surface grafting and is prepared for sulfonated graphene powder, then sulfonate polybenzimidazole has been synthesized by polymerization reaction, poly-vinyl alcohol solution, sulfonate polybenzimidazole solution and sulfonated graphene powder are mixed again and dispersed, and carry out cross-linking reaction, casting film-forming and drying are finally carried out, the crosslinking proton exchange membrane for vanadium cell is made.Proton exchange membrane prepared by the present invention not only has good proton conductivity, but also can effectively reduce the transmitance of vanadium ion, while chemical stability, satisfactory mechanical property, water absorption rate are lower.
Description
Technical field
The invention belongs to the technical fields of vanadium cell proton exchange membrane, provide a kind of cross-linking type proton for vanadium cell
Exchange membrane and preparation method.
Background technique
With the increasingly exhausted and corresponding environmental problem of traditional energy, the benefit of the renewable energy such as wind energy, solar energy
With causing people widely to pay close attention to and be rapidly developed, while the stable power-supplying to guarantee renewable energy, overcome it intrinsic
Problem, more and more electric power storage energy storage technologies are developed and are used, wherein flow battery as extensive energy storage technology one
Kind solution, also obtains remarkable progress in recent years.Wherein, all-vanadium flow battery is used as a kind of most representative flow battery
Type becomes research hotspot in recent years.
Vanadium cell full name is vanadium redox battery, be a kind of active material is in circulate the oxidation of liquid also
Primary battery.Compared with other electrochmical power sources, vanadium cell has apparent superiority, and major advantage is as follows: power is big, capacity is big,
It is high-efficient, the service life is long, fast response time, can momentary charge, highly-safe, at low cost, addressing freedom degree is big, can Full automatic sealing
Operation, it is pollution-free.Therefore, the development and application of vanadium cell has attracted much attention.
The critical component of vanadium cell includes electrolyte, electrode, proton exchange membrane etc., wherein proton exchange membrane is vanadium cell
Critical material, not only the vanadium ion of different valence state is separated in proton exchange membrane two sides, also to guarantee H+In film from
By passing through, it is largely fixed the performance superiority and inferiority of vanadium cell.Currently, the proton exchange membrane for being widely used in vanadium cell is main
For the Nafion series membranes of perfluorosulfonic acid type proton exchange membrane, especially DuPont Corporation, such as Nafion117 film, but by
High in the vanadium ion transmitance of Nafion series membranes, water absorption rate is high, constrains the further development and application of vanadium cell.Therefore, it grinds
Study carefully attention of the exploitation more excellent Novel electrolytic plasma membrane of performance by researcher.
Now widely used Nafion117 film has the defect that vanadium ion transmitance is high and water absorption rate is high, therefore develops
A kind of low vanadium ion transmitance, proton exchange membrane of low water absorption for vanadium cell, has great significance.
Summary of the invention
As it can be seen that now widely used Nafion117 film has the defect that vanadium ion transmitance is high and water absorption rate is high.For
Such case, the present invention propose a kind of crosslinking proton exchange membrane and preparation method for vanadium cell, proton exchange obtained
Film not only has good proton conductivity, but also can effectively reduce the transmitance of vanadium ion, while chemical stability, machinery
Functional, water absorption rate is lower.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of preparation method of the crosslinking proton exchange membrane for vanadium cell, the specific steps of the proton exchange film preparation are such as
Under:
(1) graphene oxide powder and stearic acid are mediated, is then dispersed in deionized water, p-aminobenzene sulfonic acid is added
And sulfonated graphene powder is made then through suction filtration, washing, vacuum drying in N, N'- dicyclohexylcarbodiimide, heating reaction；
(2) in lasting nitrogen atmosphere, phosphorus pentoxide powder is added in phosphoric acid, polyphosphoric acids solvent is made in stirring, so
Reducing agent, 3,3'- diaminobenzidine and 5-sodium sulfo isophthalate are added afterwards, increase temperature and is stirred to react, reaction knot
2 ~ 4h of product is impregnated using dilute hydrochloric acid after beam, then is washed with deionized, and be dried in vacuo, dimethyl acetamide is further added
In dissolved by heating, be made mass concentration be 3 ~ 5% sulfonate polybenzimidazole solution；
(3) polyvinyl alcohol is dissolved in deionized water, sulfonated graphene powder made from step (1), ultrasonic disperse is then added
Uniformly, sulfonate polybenzimidazole solution made from step (2) is added, pH to 2 ~ 3 is adjusted, crosslinking agent, heating stirring one is added
It fixes time, and standing and defoaming, then the casting film-forming on base material, it is dry, the cross-linking type proton exchange for vanadium cell is made
Film.
Preferably, the parts by weight of step (1) each raw material are, 10 ~ 20 parts by weight of graphene oxide powder, stearic acid 5 ~
8 parts by weight, 63 ~ 79 parts by weight of deionized water, 4 ~ 6 parts by weight of p-aminobenzene sulfonic acid, N, 2 ~ 3 weight of N'- dicyclohexylcarbodiimide
Measure part.
Preferably, the temperature of step (1) described reaction is 70 ~ 80 DEG C, and the time is 3 ~ 5h.
Preferably, step (2) reducing agent is potassium borohydride, sodium borohydride, sodium sulfite, potassium sulfite, sulfuric acid Asia
At least one of iron.
Preferably, the parts by weight of each raw material in step (2) described polymerization reaction system are, phosphorus pentoxide powder 37 ~
58 parts by weight, 8 ~ 25 parts by weight of phosphatase 11,4 ~ 8 parts by weight of reducing agent, 10 ~ 15 parts by weight of 3,3'-diaminobenzidine, isophthalic two
10 ~ 15 parts by weight of formic acid -5- sodium sulfonate.
Preferably, the temperature of step (2) described reaction is 170 ~ 190 DEG C, and the time is 4 ~ 6h.
Preferably, step (3) crosslinking agent is at least one of glyoxal, glutaraldehyde.
Preferably, the parts by weight of step (3) each raw material are 3 ~ 5 parts by weight of polyvinyl alcohol, 61 ~ 75 weight of deionized water
Measure part, 1 ~ 2 parts by weight of sulfonated graphene powder, 20 ~ 30 parts by weight of sulfonate polybenzimidazole solution, 1 ~ 2 parts by weight of crosslinking agent.
Preferably, step (3) heating temperature be 80 ~ 90 DEG C, the time be 10 ~ 20min, inclined heated plate be 20 ~
40min。
The present invention also provides a kind of cross-linking type proton friendships for vanadium cell that a kind of above-mentioned preparation method is prepared
Change film.The crosslinking proton exchange membrane is to first pass through surface grafting to be prepared for sulfonated graphene powder, then anti-by polymerization
Sulfonate polybenzimidazole should have been synthesized, then poly-vinyl alcohol solution, sulfonate polybenzimidazole solution and sulfonated graphene powder have been mixed
Dispersion is closed, and carries out cross-linking reaction, finally casting film-forming and drying is carried out and is made.
Polybenzimidazoles has proton conductivity in acid condition, and can effectively prevent the infiltration of vanadium ion.This
Invention contains-SO by polymerization reaction synthesis3The sulfonate polybenzimidazole of H side group, further improves proton conductivity.
After polyvinyl alcohol is blended with sulfonate polybenzimidazole, the compound of half interpenetrating network structure is obtained by cross-linking reaction
Membrane material.In the structure, not only polyvinyl alcohol molecule interchain is crosslinked, but also the part-SO of sulfonate polybenzimidazole3H base
Esterification has occurred in group, to improve the ability that proton exchange membrane prevents vanadium ion from permeating, reduces self-discharge of battery, improves electricity
Flow efficiency.Meanwhile the formation of cross-linked structure improves the chemical stability of composite membrane.
It is grafted stearic acid in surface of graphene oxide by mediating, then in N, the condensation of N'- dicyclohexylcarbodiimide
Under facilitation, amidation process occurs for stearic acid and p-aminobenzene sulfonic acid, by-SO3H group introduces surface of graphene oxide,
Make the proton exchange membrane for adulterating graphene oxide that there is stronger proton conductivity.Further, the modified oxidation stone in surface
Black alkene and polymer have better compatibility, are conducive to the evenly dispersed of graphene oxide.
As it can be seen that in polyvinyl alcohol-sulfonate polybenzimidazole-sulfonated graphene composite membrane obtained, the master of cross-linked structure
Body is made of polyvinyl alcohol molecule chain, the part-SO of sulfonate polybenzimidazole3H participates in esterification, and sulfonated graphene contains
Measure it is low so that strand it is total sulfonation degree it is lower, it is therefore prevented that due to the presence of a large amount of sulfonic acid groups cause vanadium ion transmitance increase
Add, water absorption rate increase, mechanical properties decrease the problems such as, make composite membrane under the premise of maintaining good proton conductivity, can
Effectively prevent the infiltration of vanadium ion.
It is and existing in conclusion the present invention provides a kind of crosslinking proton exchange membrane and preparation method for vanadium cell
There is technology to compare, the feature and excellent effect protruded is:
1. crosslinking proton exchange membrane prepared by the present invention not only has good proton conductivity, but also can effectively reduce
The transmitance of vanadium ion.
2. crosslinking proton exchange membrane prepared by the present invention, there is good chemical stability, mechanical performance, water absorption rate compared with
It is low.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) graphene oxide powder and stearic acid are mediated, is then dispersed in deionized water, p-aminobenzene sulfonic acid is added
And sulfonated graphene powder is made then through suction filtration, washing, vacuum drying in N, N'- dicyclohexylcarbodiimide, heating reaction；
The temperature of reaction is 76 DEG C, time 4.5h；The parts by weight of each raw material are 14 parts by weight of graphene oxide powder, 7 weight of stearic acid
Measure part, 72 parts by weight of deionized water, 5 parts by weight of p-aminobenzene sulfonic acid, N, 2 parts by weight of N'- dicyclohexylcarbodiimide；
(2) in lasting nitrogen atmosphere, phosphorus pentoxide powder is added in phosphoric acid, polyphosphoric acids solvent is made in stirring, so
Reducing agent, 3,3'- diaminobenzidine and 5-sodium sulfo isophthalate are added afterwards, increase temperature and is stirred to react, reaction knot
Product 3h is impregnated using dilute hydrochloric acid after beam, then is washed with deionized, and be dried in vacuo, is further added in dimethyl acetamide
It is dissolved by heating, the sulfonate polybenzimidazole solution that mass concentration is 4% is made；Reducing agent is potassium borohydride；The temperature of reaction
It is 178 DEG C, time 5h；The parts by weight of each raw material in polymerization reaction system are 50 parts by weight of phosphorus pentoxide powder, phosphoric acid
20 parts by weight, 5 parts by weight of reducing agent, 13 parts by weight of 3,3'-diaminobenzidine, 12 parts by weight of 5-sodium sulfo isophthalate；
(3) polyvinyl alcohol is dissolved in deionized water, sulfonated graphene powder made from step (1), ultrasonic disperse is then added
Uniformly, sulfonate polybenzimidazole solution made from step (2) is added, pH to 2.5 is adjusted, crosslinking agent, heating stirring one is added
It fixes time, and standing and defoaming, then the casting film-forming on base material, it is dry, the cross-linking type proton exchange for vanadium cell is made
Film；Crosslinking agent is glyoxal；Heating temperature is 86 DEG C, time 14min, inclined heated plate 28min；The parts by weight of each raw material
For 4 parts by weight of polyvinyl alcohol, 70 parts by weight of deionized water, 1 parts by weight of sulfonated graphene powder, sulfonate polybenzimidazole solution
24 parts by weight, 1 parts by weight of crosslinking agent.
Embodiment 2
(1) graphene oxide powder and stearic acid are mediated, is then dispersed in deionized water, p-aminobenzene sulfonic acid is added
And sulfonated graphene powder is made then through suction filtration, washing, vacuum drying in N, N'- dicyclohexylcarbodiimide, heating reaction；
The temperature of reaction is 720 DEG C, time 4.5h；The parts by weight of each raw material are 12 parts by weight of graphene oxide powder, stearic acid 6
Parts by weight, 75 parts by weight of deionized water, 5 parts by weight of p-aminobenzene sulfonic acid, N, 2 parts by weight of N'- dicyclohexylcarbodiimide；
(2) in lasting nitrogen atmosphere, phosphorus pentoxide powder is added in phosphoric acid, polyphosphoric acids solvent is made in stirring, so
Reducing agent, 3,3'- diaminobenzidine and 5-sodium sulfo isophthalate are added afterwards, increase temperature and is stirred to react, reaction knot
Product 2.5h is impregnated using dilute hydrochloric acid after beam, then is washed with deionized, and be dried in vacuo, dimethyl acetamide is further added
In dissolved by heating, be made mass concentration be 3.5% sulfonate polybenzimidazole solution；Reducing agent is sodium borohydride；Reaction
Temperature is 175 DEG C, time 5.5h；The parts by weight of each raw material in polymerization reaction system are 53 weight of phosphorus pentoxide powder
Part, 20 parts by weight of phosphoric acid, 5 parts by weight of reducing agent, 11 parts by weight of 3,3'-diaminobenzidine, 5-sodium sulfo isophthalate 11
Parts by weight；
(3) polyvinyl alcohol is dissolved in deionized water, sulfonated graphene powder made from step (1), ultrasonic disperse is then added
Uniformly, sulfonate polybenzimidazole solution made from step (2) is added, pH to 2 is adjusted, crosslinking agent is added, heating stirring is certain
It is time, and standing and defoaming, then the casting film-forming on base material, dry, the crosslinking proton exchange membrane for vanadium cell is made；
Crosslinking agent is glutaraldehyde；Heating temperature is 82 DEG C, time 18min, inclined heated plate 34min；The parts by weight of each raw material are to gather
3 parts by weight of vinyl alcohol, 72 parts by weight of deionized water, 2 parts by weight of sulfonated graphene powder, 22 weight of sulfonate polybenzimidazole solution
Part, 1 parts by weight of crosslinking agent.
Embodiment 3
(1) graphene oxide powder and stearic acid are mediated, is then dispersed in deionized water, p-aminobenzene sulfonic acid is added
And sulfonated graphene powder is made then through suction filtration, washing, vacuum drying in N, N'- dicyclohexylcarbodiimide, heating reaction；
The temperature of reaction is 78 DEG C, time 3.5h；The parts by weight of each raw material are 18 parts by weight of graphene oxide powder, 7 weight of stearic acid
Measure part, 66 parts by weight of deionized water, 6 parts by weight of p-aminobenzene sulfonic acid, N, 3 parts by weight of N'- dicyclohexylcarbodiimide；
(2) in lasting nitrogen atmosphere, phosphorus pentoxide powder is added in phosphoric acid, polyphosphoric acids solvent is made in stirring, so
Reducing agent, 3,3'- diaminobenzidine and 5-sodium sulfo isophthalate are added afterwards, increase temperature and is stirred to react, reaction knot
Product 3.5h is impregnated using dilute hydrochloric acid after beam, then is washed with deionized, and be dried in vacuo, dimethyl acetamide is further added
In dissolved by heating, be made mass concentration be 4.5% sulfonate polybenzimidazole solution；Reducing agent is sodium sulfite；Reaction
Temperature is 185 DEG C, time 4.5h；The parts by weight of each raw material in polymerization reaction system are 43 weight of phosphorus pentoxide powder
Part, 22 parts by weight of phosphoric acid, 7 parts by weight of reducing agent, 14 parts by weight of 3,3'-diaminobenzidine, 5-sodium sulfo isophthalate 14
Parts by weight；
(3) polyvinyl alcohol is dissolved in deionized water, sulfonated graphene powder made from step (1), ultrasonic disperse is then added
Uniformly, sulfonate polybenzimidazole solution made from step (2) is added, pH to 3 is adjusted, crosslinking agent is added, heating stirring is certain
It is time, and standing and defoaming, then the casting film-forming on base material, dry, the crosslinking proton exchange membrane for vanadium cell is made；
Crosslinking agent is glyoxal；Heating temperature is 88 DEG C, time 12min, inclined heated plate 25min；The parts by weight of each raw material are to gather
5 parts by weight of vinyl alcohol, 64 parts by weight of deionized water, 2 parts by weight of sulfonated graphene powder, 27 weight of sulfonate polybenzimidazole solution
Part, 2 parts by weight of crosslinking agent.
Embodiment 4
(1) graphene oxide powder and stearic acid are mediated, is then dispersed in deionized water, p-aminobenzene sulfonic acid is added
And sulfonated graphene powder is made then through suction filtration, washing, vacuum drying in N, N'- dicyclohexylcarbodiimide, heating reaction；
The temperature of reaction is 70 DEG C, time 5h；The parts by weight of each raw material are 10 parts by weight of graphene oxide powder, 5 weight of stearic acid
Part, 79 parts by weight of deionized water, 4 parts by weight of p-aminobenzene sulfonic acid, N, 2 parts by weight of N'- dicyclohexylcarbodiimide；
(2) in lasting nitrogen atmosphere, phosphorus pentoxide powder is added in phosphoric acid, polyphosphoric acids solvent is made in stirring, so
Reducing agent, 3,3'- diaminobenzidine and 5-sodium sulfo isophthalate are added afterwards, increase temperature and is stirred to react, reaction knot
Product 2h is impregnated using dilute hydrochloric acid after beam, then is washed with deionized, and be dried in vacuo, is further added in dimethyl acetamide
It is dissolved by heating, the sulfonate polybenzimidazole solution that mass concentration is 3% is made；Reducing agent is potassium sulfite；The temperature of reaction
It is 170 DEG C, time 6h；The parts by weight of each raw material in polymerization reaction system are 58 parts by weight of phosphorus pentoxide powder, phosphoric acid
18 parts by weight, 4 parts by weight of reducing agent, 10 parts by weight of 3,3'-diaminobenzidine, 10 parts by weight of 5-sodium sulfo isophthalate；
(3) polyvinyl alcohol is dissolved in deionized water, sulfonated graphene powder made from step (1), ultrasonic disperse is then added
Uniformly, sulfonate polybenzimidazole solution made from step (2) is added, pH to 2 is adjusted, crosslinking agent is added, heating stirring is certain
It is time, and standing and defoaming, then the casting film-forming on base material, dry, the crosslinking proton exchange membrane for vanadium cell is made；
Crosslinking agent is glutaraldehyde；Heating temperature is 80 DEG C, time 20min, inclined heated plate 40min；The parts by weight of each raw material are to gather
3 parts by weight of vinyl alcohol, 75 parts by weight of deionized water, 1 parts by weight of sulfonated graphene powder, 20 weight of sulfonate polybenzimidazole solution
Part, 1 parts by weight of crosslinking agent.
Embodiment 5
(1) graphene oxide powder and stearic acid are mediated, is then dispersed in deionized water, p-aminobenzene sulfonic acid is added
And sulfonated graphene powder is made then through suction filtration, washing, vacuum drying in N, N'- dicyclohexylcarbodiimide, heating reaction；
The temperature of reaction is 80 DEG C, time 3h；The parts by weight of each raw material are 20 parts by weight of graphene oxide powder, 8 weight of stearic acid
Part, 63 parts by weight of deionized water, 6 parts by weight of p-aminobenzene sulfonic acid, N, 3 parts by weight of N'- dicyclohexylcarbodiimide；
(2) in lasting nitrogen atmosphere, phosphorus pentoxide powder is added in phosphoric acid, polyphosphoric acids solvent is made in stirring, so
Reducing agent, 3,3'- diaminobenzidine and 5-sodium sulfo isophthalate are added afterwards, increase temperature and is stirred to react, reaction knot
Product 4h is impregnated using dilute hydrochloric acid after beam, then is washed with deionized, and be dried in vacuo, is further added in dimethyl acetamide
It is dissolved by heating, the sulfonate polybenzimidazole solution that mass concentration is 5% is made；Reducing agent is potassium sulfite；The temperature of reaction
It is 190 DEG C, time 4h；The parts by weight of each raw material in polymerization reaction system are 37 parts by weight of phosphorus pentoxide powder, phosphoric acid
25 parts by weight, 8 parts by weight of reducing agent, 15 parts by weight of 3,3'-diaminobenzidine, 15 parts by weight of 5-sodium sulfo isophthalate；
(3) polyvinyl alcohol is dissolved in deionized water, sulfonated graphene powder made from step (1), ultrasonic disperse is then added
Uniformly, sulfonate polybenzimidazole solution made from step (2) is added, pH to 3 is adjusted, crosslinking agent is added, heating stirring is certain
It is time, and standing and defoaming, then the casting film-forming on base material, dry, the crosslinking proton exchange membrane for vanadium cell is made；
Crosslinking agent is glyoxal；Heating temperature is 90 DEG C, time 10min, inclined heated plate 20min；The parts by weight of each raw material are to gather
5 parts by weight of vinyl alcohol, 61 parts by weight of deionized water, 2 parts by weight of sulfonated graphene powder, 30 weight of sulfonate polybenzimidazole solution
Part, 2 parts by weight of crosslinking agent.
Embodiment 6
(1) graphene oxide powder and stearic acid are mediated, is then dispersed in deionized water, p-aminobenzene sulfonic acid is added
And sulfonated graphene powder is made then through suction filtration, washing, vacuum drying in N, N'- dicyclohexylcarbodiimide, heating reaction；
The temperature of reaction is 75 DEG C, time 4h；The parts by weight of each raw material are 15 parts by weight of graphene oxide powder, 6 weight of stearic acid
Part, 71 parts by weight of deionized water, 5 parts by weight of p-aminobenzene sulfonic acid, N, 3 parts by weight of N'- dicyclohexylcarbodiimide；
(2) in lasting nitrogen atmosphere, phosphorus pentoxide powder is added in phosphoric acid, polyphosphoric acids solvent is made in stirring, so
Reducing agent, 3,3'- diaminobenzidine and 5-sodium sulfo isophthalate are added afterwards, increase temperature and is stirred to react, reaction knot
Product 3h is impregnated using dilute hydrochloric acid after beam, then is washed with deionized, and be dried in vacuo, is further added in dimethyl acetamide
It is dissolved by heating, the sulfonate polybenzimidazole solution that mass concentration is 4% is made；Reducing agent is ferrous sulfate；The temperature of reaction
It is 180 DEG C, time 5h；The parts by weight of each raw material in polymerization reaction system are 48 parts by weight of phosphorus pentoxide powder, phosphoric acid
22 parts by weight, 6 parts by weight of reducing agent, 12 parts by weight of 3,3'-diaminobenzidine, 12 parts by weight of 5-sodium sulfo isophthalate；
(3) polyvinyl alcohol is dissolved in deionized water, sulfonated graphene powder made from step (1), ultrasonic disperse is then added
Uniformly, sulfonate polybenzimidazole solution made from step (2) is added, pH to 2.5 is adjusted, crosslinking agent, heating stirring one is added
It fixes time, and standing and defoaming, then the casting film-forming on base material, it is dry, the cross-linking type proton exchange for vanadium cell is made
Film；Crosslinking agent is glutaraldehyde；Heating temperature is 85 DEG C, time 15min, inclined heated plate 30min；The parts by weight of each raw material
For 4 parts by weight of polyvinyl alcohol, 68 parts by weight of deionized water, 1 parts by weight of sulfonated graphene powder, sulfonate polybenzimidazole solution
25 parts by weight, 2 parts by weight of crosslinking agent.
Comparative example 1
Commercially available Nafion117 film.
Performance test:
(1) proton exchange membrane produced by the present invention proton conductivity: is utilized into H2SO4After solution impregnates, it is installed in electrolytic cell
Between, using platinum electrode as working electrode, carried out in CHI660 electrochemical workstation using the two poles of the earth AC impedence method, scan frequency is
1 ~ 100kHz, disturbance voltage 5mV are tested and are calculated proton conductivity；
(2) vanadium ion transmitance: proton exchange membrane produced by the present invention is placed between two compartments in left and right, left room is added
1mol/L VOSO4With 2mol/L H2SO4Mixed liquor, right ventricle be added 1mol/L MgSO4With 2mol/L H2SO4Mixed liquor,
Mixing test at room temperature tests the concentration of different valence state vanadium ion after a certain period of time using ultraviolet-visible spectrophotometer, according to
Membrane area and the concentration changing value of time calculate vanadium ion transmitance；
(3) water absorption rate: taking the sample of the proton exchange membrane produced by the present invention of 1cm × 2cm, then correct amount after drying soaks
Enter in 30 DEG C of deionized water for 24 hours, blot the water of film surface after taking-up rapidly using filter paper, weight after water suction is weighed, according to preceding
The ratio of the difference of weight and initial mass afterwards calculates water absorption rate.
The data obtained is as shown in table 1.
Table 1:
Claims (10)
1. a kind of preparation method of the crosslinking proton exchange membrane for vanadium cell, which is characterized in that the proton exchange membrane system
It is standby that specific step is as follows:
(1) graphene oxide powder and stearic acid are mediated, is then dispersed in deionized water, p-aminobenzene sulfonic acid is added
And sulfonated graphene powder is made then through suction filtration, washing, vacuum drying in N, N'- dicyclohexylcarbodiimide, heating reaction；
(2) in lasting nitrogen atmosphere, phosphorus pentoxide powder is added in phosphoric acid, polyphosphoric acids solvent is made in stirring, so
Reducing agent, 3,3'- diaminobenzidine and 5-sodium sulfo isophthalate are added afterwards, increase temperature and is stirred to react, reaction knot
2 ~ 4h of product is impregnated using dilute hydrochloric acid after beam, then is washed with deionized, and be dried in vacuo, dimethyl acetamide is further added
In dissolved by heating, be made mass concentration be 3 ~ 5% sulfonate polybenzimidazole solution；
(3) polyvinyl alcohol is dissolved in deionized water, sulfonated graphene powder made from step (1), ultrasonic disperse is then added
Uniformly, sulfonate polybenzimidazole solution made from step (2) is added, pH to 2 ~ 3 is adjusted, crosslinking agent, heating stirring one is added
It fixes time, and standing and defoaming, then the casting film-forming on base material, it is dry, the cross-linking type proton exchange for vanadium cell is made
Film.
2. a kind of preparation method of the crosslinking proton exchange membrane for vanadium cell according to claim 1, it is characterised in that:
The parts by weight of step (1) each raw material are 10 ~ 20 parts by weight of graphene oxide powder, 5 ~ 8 parts by weight of stearic acid, deionization
63 ~ 79 parts by weight of water, 4 ~ 6 parts by weight of p-aminobenzene sulfonic acid, N, 2 ~ 3 parts by weight of N'- dicyclohexylcarbodiimide.
3. a kind of preparation method of the crosslinking proton exchange membrane for vanadium cell according to claim 1, it is characterised in that:
The temperature of step (1) described reaction is 70 ~ 80 DEG C, and the time is 3 ~ 5h.
4. a kind of preparation method of the crosslinking proton exchange membrane for vanadium cell according to claim 1, it is characterised in that:
Step (2) reducing agent is at least one of potassium borohydride, sodium borohydride, sodium sulfite, potassium sulfite, ferrous sulfate.
5. a kind of preparation method of the crosslinking proton exchange membrane for vanadium cell according to claim 1, it is characterised in that:
The parts by weight of each raw material in step (2) described polymerization reaction system are, 37 ~ 58 parts by weight of phosphorus pentoxide powder, phosphatase 11 8 ~
25 parts by weight, 4 ~ 8 parts by weight of reducing agent, 10 ~ 15 parts by weight of 3,3'-diaminobenzidine, 5-sodium sulfo isophthalate 10 ~
15 parts by weight.
6. a kind of preparation method of the crosslinking proton exchange membrane for vanadium cell according to claim 1, it is characterised in that:
The temperature of step (2) described reaction is 170 ~ 190 DEG C, and the time is 4 ~ 6h.
7. a kind of preparation method of the crosslinking proton exchange membrane for vanadium cell according to claim 1, it is characterised in that:
Step (3) crosslinking agent is at least one of glyoxal, glutaraldehyde.
8. a kind of preparation method of the crosslinking proton exchange membrane for vanadium cell according to claim 1, it is characterised in that:
The parts by weight of step (3) each raw material are 3 ~ 5 parts by weight of polyvinyl alcohol, 61 ~ 75 parts by weight of deionized water, sulfonated graphene
1 ~ 2 parts by weight of powder, 20 ~ 30 parts by weight of sulfonate polybenzimidazole solution, 1 ~ 2 parts by weight of crosslinking agent.
9. a kind of preparation method of the crosslinking proton exchange membrane for vanadium cell according to claim 1, it is characterised in that:
Step (3) heating temperature is 80 ~ 90 DEG C, and the time is 10 ~ 20min, and inclined heated plate is 20 ~ 40min.
10. a kind of cross-linking type proton exchange for vanadium cell that any one of claim 1 ~ 9 preparation method is prepared
Film.
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