CN106602112B - A kind of method of modifying of the proton exchange membrane for all-vanadium flow battery - Google Patents
A kind of method of modifying of the proton exchange membrane for all-vanadium flow battery Download PDFInfo
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- CN106602112B CN106602112B CN201611167943.9A CN201611167943A CN106602112B CN 106602112 B CN106602112 B CN 106602112B CN 201611167943 A CN201611167943 A CN 201611167943A CN 106602112 B CN106602112 B CN 106602112B
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
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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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- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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Abstract
The present invention relates to a kind of method of modifying of proton exchange membrane for all-vanadium flow battery, are related to battery technology field.Itself the following steps are included: S1, graphite oxide preparation: use natural graphite as raw material, add the concentrated sulfuric acid and phosphoric acid mixing, react at low temperature, potassium permanganate is added and is aoxidized, is freeze-dried, obtains graphite oxide；The preparation of S2, sulfoxidation graphite: sulfonic group is connected on graphite oxide by diazonium salt metathesis with p-aminobenzene sulfonic acid, obtains sulfoxidation graphite；The preparation of S3, modified carboxy methyl cellulose sodium film: in deionized water by sulfoxidation graphite dispersion, addition carboxymethylcellulose sodium solution is uniformly mixed, and coating film forming and drying obtain modified carboxy methyl cellulose sodium film.The method of the present invention is simple and reliable, strong operability, and the modified carboxy methyl cellulose sodium film prepared using this method is at low cost, and water imbibition and vanadium ion permeability are low, and ion exchange capacity, proton conductive and selectivity are high, and comprehensive performance is good.
Description
Technical field
The present invention relates to a kind of method of modifying of proton exchange membrane for all-vanadium flow battery, are related to battery technology neck
Domain.
Background technique
With the development of the social economy, the utilization of renewable energy is increasingly paid attention to, develop matched extensive efficient
Energy storage device have become and solve the inefficient effective way of renewable energy utilization.All-vanadium flow battery energy storage device conduct
A kind of safe, low in cost, reliable large-scale renewable energy energy storage device, has extended cycle life, effect on environment is small, can
The effective storage realized to renewable energy.
Wherein, proton exchange membrane is the core component of all-vanadium flow battery, proton exchange used in all-vanadium flow battery
Film is mainly Nafion membrane, and chemical stability is good, and proton conductivity is high, but there is also resistance vanadium performance is poor, cost price is high
The problems such as.Therefore, being modified to Nafion membrane is highly desirable, and modified method is mainly around the infiltration for how reducing vanadium ion
Rate expansion.Modified means are mainly include the following types: double teeming system after introducing organic or inorganic filler, being blended with other polymers
Standby composite membrane such as modifies at the surface fluorocarbon polymer Nafion.Nafion membrane is carried out by above several method of modifying
After modification, the resistance vanadium performance of Nafion film is all greatly improved, but while resistance vanadium performance boost, Nafion
But there is different degrees of decline in the proton conductive of film, and since the Costco Wholesale of Nafion is too high, modified cost is simultaneously
Do not decline how much, be still to restrict its important bottleneck for applying in all-vanadium flow battery.
In recent years, lower-cost not fluorine-containing type cation-exchange membrane has obtained extensive concern.For example, film forming
Good, nonfluorinated sodium carboxymethylcellulose cheap and easy to get is widely used as the diaphragm of all-vanadium flow battery by researcher, still, the film
Water imbibition it is too high, the swelling ratio of film is excessive, and proton conductive is lower, be far below Nafion membrane, in addition, vanadium ion permeability
Also higher.
In conclusion being badly in need of providing a kind of method of modifying of proton exchange membrane for all-vanadium flow battery, and then prepare
At low cost out, good film-forming property, water imbibition is low, and ion exchange capacity is high, resistance vanadium, proton conductive and selective good compound matter
Proton exchange.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of proton exchange membrane for all-vanadium flow battery
Method of modifying, the method for modifying is simple and reliable, strong operability, using method of modifying prepare compound proton exchange membrane cost
Low, good film-forming property, water imbibition is low, and ion exchange capacity is high, and resistance vanadium, proton conductive and selectivity are good.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
A kind of method of modifying of the proton exchange membrane for all-vanadium flow battery, comprising the following steps:
The preparation of S1, graphite oxide: it using natural graphite as raw material, adds the concentrated sulfuric acid and phosphoric acid is uniformly mixed, low
It is reacted under temperature, adds potassium permanganate and aoxidized, is finally freeze-dried, obtain graphite oxide；
The preparation of S2, sulfoxidation graphite: using p-aminobenzene sulfonic acid by diazonium salt metathesis in the step S1
Sulfonic group is connected on the graphite oxide of preparation, obtains sulfoxidation graphite；
The preparation of S3, modified carboxy methyl cellulose sodium film: the step S2 sulfoxidation graphite dispersion prepared is existed
In deionized water, addition carboxymethylcellulose sodium solution is uniformly mixed, and coating film forming and drying obtain modified carboxy methyl cellulose
Sodium film.
A kind of improvement as the present invention for the method for modifying of the proton exchange membrane of all-vanadium flow battery, the step S3
After further include step S4:
The preparation of S4, compound proton exchange membrane: the modified carboxy methyl cellulose sodium film of step S3 preparation is repeated into n
Secondary dipping diallyl dimethyl ammoniumchloride and poly (sodium 4-styrenesulfonate) solution obtain compound proton exchange membrane, wherein n
For the integer more than or equal to 1.
A kind of improvement as the present invention for the method for modifying of the proton exchange membrane of all-vanadium flow battery, the step S3
The following steps are included:
S31, sulfoxidation graphite is dissolved in deionized water, stirs and is ultrasonically treated, it is molten that sulfoxidation graphite is made
Liquid；
S32, sodium carboxymethylcellulose is dissolved in deionized water, and with sulfoxidation stone made from the step S31
Black solution mixing, adds crosslinking agent later, stirs evenly, obtain mixed solution；
S33, ultrasound and stirring are carried out to mixed solution made from the step S32, are respectively repeated as many times；
S34, the finally obtained mixed liquor of step S33 is placed in poly (methyl methacrylate) plate film forming area, it is dry, film is made
Head product；
S35, activation processing in sulfuric acid is placed in film head product made from the step S34, rinsed, removal film surface is residual
Remaining sulfuric acid obtains modified carboxy methyl cellulose sodium film.
A kind of improvement as the present invention for the method for modifying of the proton exchange membrane of all-vanadium flow battery, the step
The quality of sulfoxidation graphite in S31 is the 1%-9% of the quality of sodium carboxymethylcellulose in step S32；
Preferably, the quality of the sulfoxidation graphite in the step S31 is the matter of sodium carboxymethylcellulose in step S32
The 7% of amount.
A kind of improvement as the present invention for the method for modifying of the proton exchange membrane of all-vanadium flow battery, the step
Crosslinking agent in S32 is glutaraldehyde, and the mass fraction of glutaraldehyde is 2%.
A kind of improvement as the present invention for the method for modifying of the proton exchange membrane of all-vanadium flow battery, the step
A ultrasonic time in S33 is 20-60min, and a mixing time is 10-30min；
Preferably, a ultrasonic time in the step S33 is 40min, and a mixing time is 20min.
A kind of improvement as the present invention for the method for modifying of the proton exchange membrane of all-vanadium flow battery, the step
Drying temperature in S34 is 50-90 DEG C, drying time 12-36h；
Preferably, the drying temperature in the step S34 is 70 DEG C, and drying time is for 24 hours.
A kind of improvement as the present invention for the method for modifying of the proton exchange membrane of all-vanadium flow battery, the step
Sulfuric acid concentration in S35 is 0.5-2mol/L, and the activation processing time is 24-48h；
Preferably, the sulfuric acid concentration in the step S35 is 1mol/L, and the activation processing time is 36h.
A kind of improvement as the present invention for the method for modifying of the proton exchange membrane of all-vanadium flow battery, the step S4
It is specific as follows:
Modified carboxy methyl cellulose sodium film after activation is first dipped into diallyl dimethyl ammoniumchloride solution
Reaction takes out rinse surface later, then immerses in poly (sodium 4-styrenesulfonate) solution and react, and impregnates the above two solution n times repeatedly,
It finally takes out and rinses, obtain compound proton exchange membrane.
A kind of improvement as the present invention for the method for modifying of the proton exchange membrane of all-vanadium flow battery, the step S4
In the mass fraction of diallyl dimethyl ammoniumchloride be 1%-10%, the mass fraction of poly (sodium 4-styrenesulfonate) is
1%-10%；
Preferably, the mass fraction of the diallyl dimethyl ammoniumchloride in the step S4 is 2%, is gathered to styrene
The mass fraction of sodium sulfonate is 3%.
(3) beneficial effect
The beneficial effects of the present invention are:
The present invention is mixed using sulfoxidation graphite with sodium carboxymethylcellulose original solution, prepares proton exchange membrane, i.e.,
Modified carboxy methyl cellulose sodium film.Compared with existing CMC-Na original film, modified modified carboxy methyl cellulose sodium obtained
Film is at low cost, and water imbibition and vanadium ion permeability are low, and ion exchange capacity, proton conductive and selectivity are high, comprehensive performance
It is good.For example, being 20mAcm in current density-2In the case where, the coulomb of modified carboxy methyl cellulose sodium film assembled battery is imitated
Rate is up to 97.1%, higher than the coulombic efficiency of CMC-Na original film assembled battery.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of the method for modifying of proton exchange membrane for all-vanadium flow battery of the invention.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair
It is bright to be described in detail.
The present invention is mixed using sulfoxidation graphite (SGO) with sodium carboxymethylcellulose (CMC-Na) original solution, is prepared
Proton exchange membrane, i.e. modified carboxy methyl cellulose sodium (SGO-CMC) film, the method for modifying is simple and reliable, strong operability.With
Existing CMC-Na original film is compared, and modified SGO-CMC proton exchange membrane obtained is at low cost, water imbibition and vanadium ion permeability
Low, ion exchange capacity, proton conductive and selectivity are high, and comprehensive performance is good.For example, being 20mAcm in current density-2's
In the case of, the coulombic efficiency of SGO-CMC proton exchange membrane assembled battery is up to 97.1%, higher than CMC-Na original film assembled battery
Coulombic efficiency.In addition, the SGO-CMC proton exchange membrane of preparation has high-temperature stability and acid resistance, it can be in high temperature and acidity
Long-term work under environment.
Especially, in order to further increase resistance vanadium performance and proton conductive, the present invention is in SGO-CMC proton exchange membrane two
Two kinds of side alternating coating diallyl dimethyl ammoniumchloride (PDDA) and poly (sodium 4-styrenesulfonate) (PSS) is respectively with positive negative electricity
SGO- [PDDA/PSS] is further made in the polyelectrolyte of lotusn(wherein, n be preparation process in repeat impregnate PDDA solution and
The number of PSS solution) compound proton exchange membrane, while to SGO- [PDDA/PSS]nThe water imbibition of compound proton exchange membrane, ion
The performances such as exchange capacity, resistance vanadium performance, proton conductive and selectivity are studied, referring specifically to following embodiment.
Embodiment 1
As shown in Figure 1, embodiment 1 provides a kind of method of modifying of proton exchange membrane for all-vanadium flow battery,
The following steps are included:
The preparation of S1, graphite oxide (GO): using natural graphite as raw material, adding the concentrated sulfuric acid and phosphoric acid be uniformly mixed,
It is reacted at low temperature, adds potassium permanganate and aoxidized, is finally freeze-dried, obtain GO.
Specifically, step S1 the following steps are included:
S11,3g natural graphite is weighed, added it in the 1000ml three-necked flask fixed.S12,360ml matter is measured
The concentrated sulfuric acid that amount score is 98% is uniformly mixed with 40ml phosphoric acid, after mixeding liquid temperature is reduced to 10 DEG C or less with ice-water bath,
It is added in the three-necked flask for filling natural graphite, and in ice-water bath, 12h is persistently stirred using mechanical stirring device, during which
The temperature in three-necked flask is kept to be lower than 20 DEG C.Under the premise of S13, the temperature in guarantee three-necked flask are lower than 20 DEG C, by 18g
Potassium permanganate is added in three-necked flask at a slow speed several times, and after mixing 30min, solution presentation is blackish green, is warming up to 50 DEG C, heat preservation is anti-
Answer 12h.S14,200ml deionized water is slowly dropped in three-necked flask with separatory funnel with the speed of 2 seconds/drop, is dripped
Bi Hou is warming up to 95 DEG C, insulation reaction 30min.S15, the reactant in three-necked flask is poured into it is containing 50ml mass fraction
In the 1000ml ice water of 30% hydrogen peroxide, quenching reacts and decomposes unreacted potassium permanganate.S16, last product is carried out
Filtering after eccentric cleaning, is lyophilized with freeze drier, finally obtains GO, spare after grind into powder.
The preparation of S2, SGO: it is connected on GO prepared by step S1 using p-aminobenzene sulfonic acid by diazonium salt metathesis
Sulfonic group obtains SGO.
Specifically, step S2 the following steps are included:
S21,0.5g sodium hydroxide is weighed, added it in 10g deionized water, it is to be mixed to after clear, it is added
2.1g p-aminobenzene sulfonic acid is reacted, and continues to stir to transparent.S22, the clear solution mixed is placed in ice salt bath, is controlled
Temperature processed at 0 DEG C hereinafter, be added 0.5g GO, and thereto be added dropwise 3ml mass fraction be 35% concentrated hydrochloric acid, after being added dropwise,
It is stirred to react 15min.S23,0.8g sodium nitrite is weighed, measures 10ml deionized water, is added dropwise in step S22 and closes after mixing
At solution in, after being added dropwise, be stirred to react 15min, obtain milky white solution.S24, obtained milky white solution is carried out
It after eccentric cleaning, is lyophilized using freeze drier, obtains SGO, it is spare after grind into powder.
The preparation of S3, SGO-CMC film: SGO dispersion prepared by step S2 in deionized water, adds CMC-Na solution
It is uniformly mixed, coating film forming and drying, obtains SGO-CMC film.
Specifically, step S3 the following steps are included:
S31,0.012g SGO is weighed, be dissolved in 20ml deionized water, after stirring 30min, be ultrasonically treated 2h, system
Obtain SGO solution.S32,1.2g CMC-Na is weighed, after it is dissolved completely in 40ml deionized water, and be ultrasonically treated
The mixing of SGO solution, is added the crosslinking agent glutaraldehyde that 0.5ml mass fraction is 2% later, and stirring for 24 hours, is uniformly mixed molten
Liquid.S33, it the mixed solution stirred evenly is put into supersonic wave cleaning machine carries out ultrasonic treatment 20min, take out later, stir
10min is repeated the process at least 3 times.S34, the film forming area that 10 × 10 × 0.6cm is crossed on clean poly (methyl methacrylate) plate, will
The mixed solution that step S33 is obtained pours into film forming area, is put into drying, drying temperature in air dry oven and is set as 50 DEG C, does
The dry time is for 24 hours, so that SGO-CMC film head product be made.S35, SGO-CMC film head product made from step S34 is taken
After out, being placed in concentration is 1molL-1Sulfuric acid in carry out activation processing for 24 hours, with deionized water wash off film surface remaining
Sulfuric acid, obtain SGO-CMC film product.
S4, will activation treated SGO-CMC film is first dipped into mass fraction be 2% PDDA solution in react
15min, later taking-up rinse surface with deionized water, are placed in deionized water and impregnate 10min, then immersing mass fraction is 3%
PSS solution in react 15min, finally taking-up is rinsed with deionized water, can be obtained compound proton exchange membrane SGO- [PDDA/
PSS]1。
It is similar with the preparation step of embodiment 1, embodiment 2-33 be the SGO by adjusting preparation process mass fraction,
Ultrasound and mixing time in step S33, the drying temperature in step S34 and time, the sulfuric acid concentration in step S35 and activation
It is multiple to prepare that the Parameter Conditions such as the frequency n of PDDA and PSS are impregnated in time, the mass fraction of PDDA, the mass fraction of PSS and repetition
It closes proton exchange membrane SGO- [PDDA/PSS]n.Embodiment 2-33 is to compound proton exchange membrane SGO- [PDDA/PSS]nPreparation feelings
Condition is specifically as shown in table 1.
Table 1: embodiment 2-33 is to compound proton exchange membrane SGO- [PDDA/PSS]nPreparation situation.
It compares with unmodified CMC-Na original film, the compound proton exchange membrane SGO- of above-described embodiment 2-33 preparation
[PDDA/PSS]nWater imbibition is low, and vanadium ion permeability is low, and ion exchange capacity, proton conductive and selectivity are high.Through studying,
Especially the mass fraction of SGO (i.e. doping), immersion number factor are to compound proton exchange membrane SGO- [PDDA/PSS]nPerformance
Influence it is more significant.
The compound proton exchange membrane SGO- [PDDA/PSS] below prepared by embodiment 5,12,19,24 and 291With CMC-Na
The properties of former film compare, and specific various performance parameters are as shown in table 2.
Table 2: compound proton exchange membrane SGO- [PDDA/PSS] prepared by embodiment 5,12,19,24 and 291With CMC-Na original
The performance indexes result of film.
From table 2 it can be seen that since SGO has certain hydrophobicity, with the increase of SGO doping, composite proton exchange
Film SGO- [PDDA/PSS]1Decline, reduce the swelling of film, while the introducing of SGO sulfonic acid group exchanges composite proton
Film SGO- [PDDA/PSS]1Ion exchange capacity improve, also promote proton conduction, improve proton conductivity and ion selection
Property.But with the increase of doping (more than 7%), SGO will appear agglomeration, reduce proton transmitting channel, compound matter
Proton exchange SGO- [PDDA/PSS]1Proton conductivity and ion selectivity decline, in addition, compound proton exchange membrane SGO-
[PDDA/PSS]1Present laminar structured, and two kinds of crystallite dimensions in film are relatively fixed, effectively inhibit the infiltration of vanadium ion.
In other words, compound proton exchange membrane SGO- [PDDA/PSS] prepared by the SGO that doping mass fraction is 7%1's
Water imbibition is low, and ion exchange capacity is high, and vanadium ion permeability is low, and proton conductive is moderate, and ion selectivity is best, whole synthesis
Performance is best.
Compound proton exchange membrane SGO- [PDDA/PSS] prepared by embodiment 24, embodiment 31-33nWith CMC-Na original film
Properties compare, specific various performance parameters are as shown in table 3.
Table 3: compound proton exchange membrane SGO- [PDDA/PSS] prepared by embodiment 24, embodiment 31-33nWith CMC-Na original
The performance indexes result of film.
From table 3 it can be seen that with the increase for impregnating frequency n repeatedly, compound proton exchange membrane SGO- [PDDA/PSS]n's
Water imbibition reduces, and ion exchange capacity reduces, and vanadium ion permeability reduces, and proton conductive reduces, and ion selectivity is better.This
It is the compound proton exchange membrane SGO- [PDDA/PSS] formed due to impregnating PDDA and PSSnWater imbibition is poor, ion exchange capacity
Not high, proton conductive is not high, with the increase of PDDA and PSS layer number, compound proton exchange membrane SGO- [PDDA/PSS]nGradually
Contact of the inner layer film with external environment has been blocked, therefore, compound proton exchange membrane SGO- [PDDA/PSS]nWater imbibition, ion
Exchange capacity and proton conductive reduce, meanwhile, film is fine and close and divides positive and negative charge layer, can effectively obstruct the infiltration of vanadium ion, make
Vanadium ion permeability is remarkably decreased.But since proton conductive declines, vanadium ion permeability is reduced, and is impregnating number repeatedly
After 2 times, compound proton exchange membrane SGO- [PDDA/PSS]nIon selectivity reduce.
In other words, reach maximum value, effect when impregnating PDDA twice and PSS, PDDA and PSS repeatedly with two membranes
It is best.
In conclusion needing to stress, when SGO doping is 7% and the number of immersion PDDA and PSS is 2 times
The compound proton exchange membrane SGO- [PDDA/PSS] of preparation2At low cost, water imbibition and vanadium ion permeability are low, and ion exchange is held
Amount, proton conductive and selectivity are high, and comprehensive performance is best.
The technical principle that detailed description of the preferred embodimentsthe present invention has been described is combined above.These descriptions are intended merely to explain the present invention
Principle, and shall not be construed in any way as a limitation of the scope of protection of the invention.Based on the explanation herein, art technology
Personnel, which do not need to make the creative labor, can associate other specific embodiments of the invention, these modes fall within this
Within the protection scope of invention.
Claims (10)
1. a kind of method of modifying of the proton exchange membrane for all-vanadium flow battery, which comprises the following steps:
The preparation of S1, graphite oxide: it using natural graphite as raw material, adds the concentrated sulfuric acid and phosphoric acid is uniformly mixed, at low temperature
It is reacted, adds potassium permanganate and aoxidized, is finally freeze-dried, obtain graphite oxide；
The preparation of S2, sulfoxidation graphite: it is prepared by diazonium salt metathesis in the step S1 using p-aminobenzene sulfonic acid
Graphite oxide on connect sulfonic group, obtain sulfoxidation graphite；
The preparation of S3, modified carboxy methyl cellulose sodium film: by the step S2 preparation sulfoxidation graphite dispersion go from
In sub- water, addition carboxymethylcellulose sodium solution is uniformly mixed, and it is thin to obtain modified carboxy methyl cellulose sodium for coating film forming and drying
Film.
2. the method for modifying for the proton exchange membrane of all-vanadium flow battery as described in claim 1, it is characterised in that: described
Further include step S4 after step S3:
The preparation of S4, compound proton exchange membrane: the modified carboxy methyl cellulose sodium film of step S3 preparation is repeated into n times leaching
Stain diallyl dimethyl ammoniumchloride solution and poly (sodium 4-styrenesulfonate) solution obtain compound proton exchange membrane, wherein n
For the integer more than or equal to 1.
3. the method for modifying for the proton exchange membrane of all-vanadium flow battery as described in claim 1, it is characterised in that: described
Step S3 the following steps are included:
S31, the step S2 sulfoxidation graphite prepared is dissolved in deionized water, stirs and be ultrasonically treated, sulphur is made
Change graphite oxide solution；
S32, sodium carboxymethylcellulose is dissolved in deionized water, and molten with sulfoxidation graphite made from the step S31
Liquid mixing, adds crosslinking agent later, stirs evenly, obtain mixed solution；
S33, ultrasound and stirring are carried out to mixed solution made from the step S32, are respectively repeated as many times；
S34, the finally obtained mixed liquor of step S33 is placed in poly (methyl methacrylate) plate film forming area, it is dry, film primiparity is made
Product；
S35, activation processing in sulfuric acid is placed in film head product made from the step S34, rinsed, removal film surface remnants'
Sulfuric acid obtains modified carboxy methyl cellulose sodium film.
4. the method for modifying for the proton exchange membrane of all-vanadium flow battery as claimed in claim 3, it is characterised in that: described
The quality of sulfoxidation graphite in step S31 is the 1%-9% of the quality of sodium carboxymethylcellulose in step S32.
5. the method for modifying for the proton exchange membrane of all-vanadium flow battery as claimed in claim 3, it is characterised in that: described
Crosslinking agent in step S32 is glutaraldehyde, and the mass fraction of glutaraldehyde is 2%.
6. the method for modifying for the proton exchange membrane of all-vanadium flow battery as claimed in claim 3, it is characterised in that: described
A ultrasonic time in step S33 is 20-60min, and a mixing time is 10-30min.
7. the method for modifying for the proton exchange membrane of all-vanadium flow battery as claimed in claim 3, it is characterised in that: described
Drying temperature in step S34 is 50-90 DEG C, drying time 12-36h.
8. the method for modifying for the proton exchange membrane of all-vanadium flow battery as claimed in claim 3, it is characterised in that: described
Sulfuric acid concentration in step S35 is 0.5-2mol/L, and the activation processing time is 24-48h.
9. the method for modifying for the proton exchange membrane of all-vanadium flow battery as claimed in claim 2, it is characterised in that: described
Step S4 is specific as follows:
It is molten that the step S3 modified carboxy methyl cellulose sodium film prepared is first dipped into diallyl dimethyl ammoniumchloride
It is reacted in liquid, takes out rinse surface later, then immerse in poly (sodium 4-styrenesulfonate) solution and react, impregnate above two solution repeatedly
N times are finally taken out and are rinsed, obtain compound proton exchange membrane.
10. the method for modifying for the proton exchange membrane of all-vanadium flow battery as claimed in claim 9, it is characterised in that: institute
The mass fraction for stating the diallyl dimethyl ammoniumchloride in step S4 is 1%-10%, the quality of poly (sodium 4-styrenesulfonate)
Score is 1%-10%.
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