CN110197918A - A kind of perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery and its preparation method and application - Google Patents
A kind of perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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Abstract
It is using perfluorinated sulfonic acid ion exchange membrane and ammonification polysulfones as material the invention discloses a kind of perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery and its preparation method and application, pass through the method for blending, the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery is prepared, the method effectively raises the vanadium ion selectivity of composite membrane, so that the composite membrane be made to have better charge-discharge performance in all-vanadium flow battery.The rigid structure of the ammonification polysulfones is conducive to increase the mechanical performance of composite membrane, this can effectively limit the expansion of composite membrane.Preparation method of the invention is simple, is effectively utilized discarded perfluorosulfonic acid proton exchange film, not only realizes waste utilization, but also saved cost.Prepared composite membrane has taken into account high ionic conductivity, and low vanadium ion permeability, dilatancy and water imbibition are applicable to all-vanadium flow battery.
Description
Technical field
The invention belongs to all-vanadium flow battery technical fields, and in particular to a kind of perfluorinated sulfonic acid used for all-vanadium redox flow battery is compound
Film and its preparation method and application.
Background technique
Flow battery is a kind of novel electrochemical energy storage technology, has high-efficient, modularized design, safety and environmental protection, dimension
The advantages such as shield is simple, operating cost is low, in wind-power electricity generation, photovoltaic power generation, power grid peak load shifting, distribution power station, smart grid etc.
Field shows application prospect outstanding.All-vanadium flow battery (Vanadium flow battery, VFB) is due to charge and discharge
High-efficient, environmental-friendly, flexible design, the advantages that highly-safe, self discharge is low, the service life is long, are most had in current flow battery
A kind of flow battery of prospect.
Battery diaphragm is one of critical material of all-vanadium flow battery, the battery diaphragm on the one hand by positive and negative anodes electrolyte every
It opens, to avoid positive and negative anodes active ion cross contamination, self discharge occurs；On the other hand the conductive ions such as proton are allowed to pass through, shape
At circuit in battery.The battery diaphragm of VFB should have the following characteristics that high ionic conductivity, make battery voltage with higher
Efficiency, to reduce the polarization phenomena of battery；High vanadium ion selectivity, makes battery coulombic efficiency with higher, reduces battery
Self discharge；Resistant to chemical etching with preferable mechanical performance, resistance to electrochemical oxidation guarantees longer service life.
The diaphragm material that commercialized vanadium cell uses both at home and abroad at present is still mainly the Nafion of E.I.Du Pont Company's exploitation
Film.In flow battery, although Nafion membrane price is more expensive and ion selectivity is poor, in ionic conductivity, mechanicalness
Energy, chemical property and service life etc. are still that current many commercialization films are incomparable.And the choosing of Nafion membrane difference
Selecting property is always to perplex the problem of people, and traditional modification is often reduced by nano-particles filled or the method for doping
Although nanochannel inside film, this method can be improved the selectivity of film, but film also can be by hydrionic conducting power
To big influence, therefore it not can effectively solve problem.And if the sulfonic acid functional group to reunite can be dispersed with basic group,
The radius that cluster will be reduced increases the selectivity of film, while can also weaken the influence to hydrogen ion conductive.
Summary of the invention
In order to improve the deficiencies in the prior art, the present invention provide a kind of perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery and its
Preparation method and purposes, the method are to pass through the side being blended with ammonification polysulfones using discarded perfluorinated sulfonic acid ion exchange membrane
Method, has prepared that consumptive material is few, and ion selectivity is good, the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery of function admirable.This method
Discarded perfluorinated sulfonic acid ion exchange membrane is rationally utilized, is effectively reduced production cost, improves perfluoro sulfonic acid membrane composite membrane
Hinder vanadium performance.
The technical solution adopted by the invention is as follows:
A kind of preparation method of perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery, includes the following steps:
(1) mixed solution of the polysulfone resin after perfluorosulfonic acid proton exchange film and ammoniated treatment is prepared；
(2) mixed solution of step (1) is contacted with substrate, is heat-treated twice, the all-vanadium flow is prepared
Battery perfluorinated sulfonic acid composite membrane.
Wherein, step (1) may include steps of: by the polysulfones tree after perfluorosulfonic acid proton exchange film and ammoniated treatment
Rouge is dissolved in organic solvent respectively, and perfluorinated sulfonic acid solution and ammonification polysulfones solution is prepared, the two is mixed, is prepared mixed
Close solution.
According to an embodiment of the invention, the perfluorosulfonic acid proton exchange film is selected from pretreated complete in step (1)
Fluosulfonic acid proton exchange membrane, or selected from discarded perfluorosulfonic acid proton exchange film, or selected from pretreated discarded
Perfluorosulfonic acid proton exchange film.
According to an embodiment of the invention, the organic solvent is n,N-Dimethylformamide, N, N- bis- in step (1)
At least one of methylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or N-Methyl pyrrolidone.
According to an embodiment of the invention, in step (1), perfluorosulfonic acid proton exchange film in the perfluorinated sulfonic acid solution
Weight concentration is 2~10wt%, the weight concentration 2 of the polysulfone resin in the ammonification polysulfones solution after ammoniated treatment~
15wt%.
According to an embodiment of the invention, in step (1), perfluorosulfonic acid proton exchange film and ammonification in the mixed solution
The weight ratio of treated polysulfone resin is (60~99.999): (0.001~40).
According to an embodiment of the invention, step (1) includes the following steps: pretreated perfluorinated sulfonic acid proton exchange
Polysulfone resin after film and ammoniated treatment is dissolved in organic solvent respectively, and perfluorinated sulfonic acid solution is prepared and ammonification polysulfones is molten
Liquid mixes the two, through 1~3h of magnetic agitation, stands 4~7h, system after 20~40min of ultrasonic disperse at a temperature of 40~80 DEG C
It is standby to obtain mixed solution.
According to an embodiment of the invention, in step (2), it can be by including but is not limited to casting, dipping, silk-screen, ink-jet
Contact of the modes such as printing, roller coating, spray painting, spraying, spin coating and/or vapor deposition by mixed solution with substrate.
According to an embodiment of the invention, the substrate is selected from glass, monocrystalline silicon, polytetrafluoroethylene (PTFE) in step (2)
(PTFE), in polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimides (PI) etc. extremely
Few one kind.
According to an embodiment of the invention, the step (2) includes the following steps: to coat the mixed solution of step (1)
To substrate surface, first time heat treatment is carried out under the conditions of 40~80 DEG C, after cooling, is carried out under 100~170 DEG C of vacuum conditions
Second of heat treatment, is prepared the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery.
According to an embodiment of the invention, the step (2) includes the following steps: to coat the mixed solution of step (1)
To substrate surface, 8~14h of heat treatment for the first time is carried out in 40~80 DEG C of baking oven, is transferred in vacuum drying oven after cooling,
Second of 3~6h of heat treatment is carried out in 100~170 DEG C of vacuum drying ovens, and the perfluorinated sulfonic acid used for all-vanadium redox flow battery is prepared
Composite membrane.
According to an embodiment of the invention, the vacuum degree of the vacuum drying oven is 0.01-0.1MPa, for example, 0.08MPa.
The present invention also provides a kind of perfluorinated sulfonic acid composite membranes used for all-vanadium redox flow battery, and the composite membrane is to pass through the above method
It is prepared.
Wherein, the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery with a thickness of 50~150 μm.
The present invention also provides a kind of purposes of perfluorinated sulfonic acid composite membrane, are used for all-vanadium flow battery.
The present invention also provides a kind of all-vanadium flow battery, the battery includes above-mentioned perfluorinated sulfonic acid composite membrane.
Beneficial outcomes of the invention are:
1. the present invention is with perfluorinated sulfonic acid ion exchange membrane (preferably discarded perfluorinated sulfonic acid ion exchange membrane) and ammonification
Polysulfones is raw material, by the method for blending, the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery is prepared, the method has
Effect improves composite membrane to the selectivity of vanadium ion, and the composite membrane is made to have better charge and discharge electrical in all-vanadium flow battery
Energy.
2. the rigid structure of ammonification polysulfones is conducive to increase the mechanical performance of composite membrane in composite membrane of the present invention, this can have
The expansion of the limitation composite membrane of effect.
3. the present invention during composite membrane of preparation, can pass through the mixed of ammonification polysulfones solution and perfluorinated sulfonic acid solution
The regulation to composite membrane is realized in the control of composition and division in a proportion example, and then realizes the controllable adjustment of the battery performance of the application composite membrane.
4. preparation method of the invention is simple, it is effectively utilized discarded perfluorosulfonic acid proton exchange film, has both been realized useless
Object utilizes, and has saved cost.Prepared composite membrane has taken into account high ionic conductivity, low vanadium ion permeability, swollen
Swollen property and water imbibition, are applicable to all-vanadium flow battery.
Detailed description of the invention
Fig. 1 is the SEM surface topography map of composite membrane prepared by embodiment 1 and comparative example 1.
Fig. 2 charging and discharging curve in all-vanadium flow battery for embodiment 1 and the composite membrane of the preparation of comparative example 1.
Specific embodiment
[preparation method of perfluorinated sulfonic acid composite membrane]
As previously mentioned, the present invention provides a kind of preparation method of perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery, including such as
Lower step:
(1) mixed solution of the polysulfone resin after perfluorosulfonic acid proton exchange film and ammoniated treatment is prepared；
(2) mixed solution of step (1) is contacted with substrate, is heat-treated twice, the all-vanadium flow is prepared
Battery perfluorinated sulfonic acid composite membrane.
In a scheme of the invention, in step (1), there is no particular limitation for the preparation method of the mixed solution,
It can be well known to a person skilled in the art a kind of method, as illustratively, can be perfluorinated sulfonic acid proton exchange
Polysulfone resin after film and ammoniated treatment is dissolved in organic solvent respectively, and perfluorinated sulfonic acid solution is prepared and ammonification polysulfones is molten
Liquid mixes the two, and mixed solution is prepared；It is also possible to for perfluorosulfonic acid proton exchange film being dissolved in organic solvent, obtains
It is dissolved in wherein to perfluorinated sulfonic acid solution, then by the polysulfone resin after ammoniated treatment；It or is by the polysulfones tree after ammoniated treatment
Liposoluble obtains ammonification polysulfones solution in organic solvent, then perfluorosulfonic acid proton exchange film is dissolved in wherein.
In a scheme of the invention, in step (1), there is no particular limitation for the perfluorosulfonic acid proton exchange film,
It is selected from any perfluorosulfonic acid proton exchange film well known in the prior art, such as selected from pretreated perfluorinated sulfonic acid
Proton exchange membrane, or selected from discarded perfluorosulfonic acid proton exchange film, or selected from pretreated discarded perfluor
Sulfonic acid proton exchange film；It will be understood by those skilled in the art that can expire for the selection of the perfluorosulfonic acid proton exchange film
After sufficient its can be dissolved in organic solvent and mix with ammonification polysulfones solution, it can be prepared described used for all-vanadium redox flow battery complete
Fluosulfonic acid composite membrane.
In a scheme of the invention, in step (1), the pretreatment can be to be well known in the prior art for useless
Any pretreatment that the perfluorosulfonic acid proton exchange film of abandoning carries out, and the discarded perfluor can be removed by the pretreatment
High price vanadium ion in sulfonic acid proton exchange film and other impurities.As illustratively, obtained discarded perfluor sulphur will be recycled
Acid ion exchange membrane shreds as 0.25cm2Left and right, immerse hydrogen peroxide solution in, at 40~100 DEG C stir 10~for 24 hours, then
It is cleaned with deionized water；Immersed in sulfuric acid solution again after cleaning, at 40~100 DEG C stir 10~for 24 hours, spend again from
Sub- water is cleaned, and pretreated perfluorosulfonic acid proton exchange film is obtained.The purpose shredded is to be able to more preferable right
Discarded perfluorosulfonic acid proton exchange film is handled, and high price vanadium ion therein and other impurities is removed.Those skilled in the art
Member it should be understood that the step of shredding not be it is necessary, similarly, the degree shredded is also not limited in 0.25cm2Left and right.
In a scheme of the invention, in step (1), the concentration of the hydrogen peroxide solution and sulfuric acid solution is not special
Restriction, the removal of high price vanadium ion may be implemented in the discarded perfluorosulfonic acid proton exchange film and to the perfluorinated sulfonic acid
The protonation of proton exchange membrane is handled.Preferably, the weight concentration of the hydrogen peroxide solution is 1~15wt%, the sulphur
The concentration of acid solution is 0.2~3M (mol/L).
In a scheme of the invention, in step (1), the polysulfone resin is selected from any point well known in the prior art
Son amount and the degree of polymerization polysulfone resin, and the ammoniated treatment be also in the prior art it is any can to polysulfone resin carry out ammonia
Change the method for processing；The ammoniated treatment be by introducing nitro on the phenyl ring of polysulfones main chain or containing the branch of nitro,
Amino is converted by nitro by reduction, that is, realizes the ammoniated treatment to polysulfone resin.The purpose of the ammoniated treatment be in order to
Make the polysulfone resin that there is preferable hydrophily, increases the compatibility between perfluorosulfonic acid proton exchange film, moreover,
Polysulfone resin after ammoniated treatment has rigid structure, can increase the mechanical performance for the composite membrane being prepared, Jin Eryou
The expansion of composite membrane is limited to effect, it is substantially increased and uses the time.
In a scheme of the invention, in step (1), the organic solvent is n,N-Dimethylformamide, N, N- bis-
At least one of methylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or N-Methyl pyrrolidone.
In a scheme of the invention, in step (1), perfluorosulfonic acid proton exchange film and ammonification in the mixed solution
The weight ratio of treated polysulfone resin is (60~99.999): (0.001~40).
In a scheme of the invention, step (1) specifically comprises the following steps: pretreated perfluorinated sulfonic acid proton
Polysulfone resin after exchange membrane and ammoniated treatment is dissolved in organic solvent respectively, and perfluorinated sulfonic acid solution and ammonification polysulfones is prepared
Solution mixes the two, and through 1~3h of magnetic agitation, 4~7h is stood at a temperature of 40~80 DEG C after 20~40min of ultrasonic disperse,
Mixed solution is prepared.
In a scheme of the invention, the weight concentration of perfluorosulfonic acid proton exchange film is in the perfluorinated sulfonic acid solution
2~10wt%.2~15wt% of weight concentration of polysulfone resin in the ammonification polysulfones solution after ammoniated treatment.
In a scheme of the invention, in step (1), organic solvent and the dissolution of perfluorosulfonic acid proton exchange film are dissolved
The organic solvent of polysulfone resin after ammoniated treatment can be same organic solvent, or two with preferable compatibility
Kind organic solvent.
In a scheme of the invention, in step (2), the mode of the contact is not limited specifically, can be realized
Prepare the purpose of the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery.It will be understood by those skilled in the art that can lead to
Cross the including but not limited to modes such as casting, dipping, silk-screen, inkjet printing, roller coating, spray painting, spraying, spin coating and/or vapor deposition
Mixed solution is contacted with substrate.As illustratively, the mixed solution is placed in substrate surface and carries out spin coating, or by substrate
It is impregnated into mixed solution and carries out immersion coating etc., or mixed solution is cast to substrate surface.
In a scheme of the invention, in step (2), the selection of the substrate is not limited specifically, can be
What is do not reacted with the composite membrane any prepares the common substrate of membrane material, for example, glass, monocrystalline silicon, polytetrafluoroethyl-ne
Alkene (PTFE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimides (PI) etc.；Together
Sample, it will be understood by those skilled in the art that the shape of the substrate does not also limit specifically, it can be right according to demand
The shape of the substrate is selected, such as can be the plane substrate (such as sheet glass, monocrystalline silicon piece) for being easy to form a film,
It is also possible to the mold with specific shape (such as cuboid or cylindrical body).
In a scheme of the invention, in step (2), the mixed solution is not specific in the thickness of substrate surface
It limits, it is ensured that the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery being prepared can be realized making for the composite membrane
With purpose, i.e., positive and negative anodes electrolyte can both be separated, avoid positive and negative anodes active ion cross contamination, self discharge occurs；Again may be used
To allow the conductive ions such as proton to pass through, to form circuit in battery.As illustratively, the mixed solution is coated to base
The thickness on material surface to guarantee the composite membrane obtained after being heat-treated twice with a thickness of 50~150 μm.
In a scheme of the invention, the step (2) specifically comprises the following steps: the mixed solution of step (1)
It is coated to substrate surface, first time heat treatment is carried out under the conditions of 40~80 DEG C, after cooling, under 100~170 DEG C of vacuum conditions
It carries out second to be heat-treated, the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery is prepared.
In a scheme of the invention, the step (2) specifically comprises the following steps: the mixed solution of step (1)
It is coated to substrate surface, 8~14h of heat treatment for the first time is carried out in 40~80 DEG C of baking oven, is transferred to vacuum drying oven after cooling
In, second of 3~6h of heat treatment is carried out in 100~170 DEG C of vacuum drying ovens, and the perfluor used for all-vanadium redox flow battery is prepared
Sulfonic acid composite membrane.
In a scheme of the invention, the vacuum degree of the vacuum drying oven is 0.01-0.1MPa, for example, 0.08MPa.
[perfluorinated sulfonic acid composite membrane]
As previously mentioned, the present invention provides a kind of perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery, the composite membrane is to pass through
What the above method was prepared.
In a scheme of the invention, the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery with a thickness of 50~150 μ
m。
[purposes of perfluorinated sulfonic acid composite membrane]
As previously mentioned, the present invention provides a kind of purposes of perfluorinated sulfonic acid composite membrane, it to be used for all-vanadium flow battery.
[all-vanadium flow battery]
As previously mentioned, the battery includes that above-mentioned perfluorinated sulfonic acid is compound the present invention also provides a kind of all-vanadium flow battery
Film.
In a scheme of the invention, the charging voltage of the all-vanadium flow battery is lower than 1.45V, and discharge voltage is higher than
1.35V。
In a scheme of the invention, the coulombic efficiency of the all-vanadium flow battery is 95% or more, and voltage efficiency is
86% or more, energy efficiency is 83% or more.
The voltage efficiency refers to the ratio of the average voltage of discharge voltage and the average voltage of charging voltage.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1
It is respectively that 5g pretreated discarded perfluorosulfonic acid proton exchange film (discarded Nafion membrane) and 5g ammonification is poly-
Sulfone is dissolved in respectively in the N-Methyl pyrrolidone solvent of 45mL, and perfluorinated sulfonic acid solution and ammonification polysulfones solution is prepared.Point
Perfluorinated sulfonic acid solution that 8mL is above-mentioned and the above-mentioned ammonification polysulfones solution mixing of 0.5mL are not taken, and 1~3h of magnetic agitation is then ultrasonic
Mixed solution is put into 4~7h of standing and defoaming in 40~80 DEG C of baking oven after 20~40min of dispersion.
The weight ratio of polysulfone resin in the mixed solution after perfluorosulfonic acid proton exchange film and ammoniated treatment is 16:1.
Uniform mixed solution is poured into mold, progress first time heat treatment, i.e., 40~80 DEG C in an oven dryings 8~
14h is transferred in vacuum drying oven after cooling, is carried out second and is heat-treated, i.e., in vacuum drying oven 100~170 DEG C of heat treatments 3~
6h, is prepared the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery after cooling, the composite membrane with a thickness of 80 μm.
It is assembled into all-vanadium flow battery using the above-mentioned perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery prepared, wherein urging
Change layer is activated carbon-fiber felt, and bipolar plates are graphite plate, and the effective area of composite membrane is 4cm2, current density 40mAcm-2, electrolysis
Vanadium ion concentration is 1.5molL in liquid-1, sulfuric acid concentration 3molL-1。
The all-vanadium flow battery is tested, test result are as follows: the coulombic efficiency of all-vanadium flow battery is 96.4%, electricity
Pressing efficiency is 89%, energy efficiency 85.8%.
Embodiment 2
Other conditions are same as Example 1, and difference is in the mixed solution, and perfluorinated sulfonic acid solution is 7mL, and ammonification is poly-
Sulfolane solution is 2mL.The weight ratio of polysulfone resin in the mixed solution after perfluorosulfonic acid proton exchange film and ammoniated treatment is
7:2。
The composite membrane being prepared with a thickness of 84 μm.
The all-vanadium flow battery is tested, test result are as follows: the coulombic efficiency of all-vanadium flow battery is 97%, voltage
Efficiency is 86%, energy efficiency 83.4%.
Embodiment 3
Other conditions are same as Example 1, and difference is in the mixed solution, and perfluorinated sulfonic acid solution is 7mL, and ammonification is poly-
Sulfolane solution is 1mL.The weight ratio of polysulfone resin in the mixed solution after perfluorosulfonic acid proton exchange film and ammoniated treatment is
7:1。
The composite membrane being prepared with a thickness of 78 μm.
The all-vanadium flow battery is tested, test result are as follows: the coulombic efficiency of all-vanadium flow battery is 95.2%, electricity
Pressing efficiency is 88%, energy efficiency 83.8%.
Comparative example 1
The pretreated discarded perfluorosulfonic acid proton exchange film of 5g is dissolved in the N-Methyl pyrrolidone solvent of 45mL
In, perfluorinated sulfonic acid solution is prepared.Take the perfluorinated sulfonic acid solution that 8.5mL is above-mentioned, 1~3h of magnetic agitation, then ultrasonic disperse
Solution is put into 4~7h of standing in 40~80 DEG C of baking oven after 20~40min.
Uniform solution is poured into mold, progress first time heat treatment, i.e., 40~80 DEG C in an oven dry 8~14h,
It is transferred in vacuum drying oven after cooling, carries out second and be heat-treated, i.e., 100~170 DEG C of 3~6h of heat treatment in vacuum drying oven,
Be prepared the perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery after cooling, the composite membrane with a thickness of 80 μm.
It is assembled into all-vanadium flow battery using the above-mentioned perfluorinated sulfonic acid composite membrane used for all-vanadium redox flow battery prepared, wherein urging
Change layer is activated carbon-fiber felt, and bipolar plates are graphite plate, and the effective area of composite membrane is 4cm2, current density 40mAcm-2, electrolysis
Vanadium ion concentration is 1.5molL in liquid-1, sulfuric acid concentration 3molL-1。
The all-vanadium flow battery is tested, test result are as follows: the coulombic efficiency of all-vanadium flow battery is 90.6%, electricity
Pressing efficiency is 90.2%, energy efficiency 81.7%.
The performance for the all-vanadium flow battery being prepared from above-described embodiment 1-3 and comparative example 1 can be seen that ammonification polysulfones
(APSF) so that the coulombic efficiency for the composite membrane being prepared has obtained significantly improving, voltage efficiency does not have for introducing
Too big variation, therefore energy efficiency has obtained significant raising.The rigid structure of the polysulfone resin of ammonification increases composite membrane
Mechanical stability reduces the dilatancy of composite membrane, migrates to show low water with the battery that the composite membrane film assembles
Rate and vanadium ion permeability.
Fig. 1 is the SEM surface topography map of composite membrane prepared by embodiment 1 and comparative example 1.
Fig. 2 charging and discharging curve in all-vanadium flow battery for embodiment 1 and the composite membrane of the preparation of comparative example 1.
From figure 1 it appears that the Nafion membrane by comparison discovery comparative example 1 is (as shown in Figure 1a) with smooth table
Face, the surface of 1 composite membrane of embodiment (as shown in Figure 1 b) occurred many white particles evenly dispersed and some lines simultaneously
Do not find phenomenon of phase separation.This illustrates that APSF is dispersed in Nafion membrane, and the two has good compatibility.
From figure 2 it can be seen that the charging voltage of the all-vanadium flow battery of embodiment 1 is lower than 1.45V, discharge voltage is higher than
1.35V.Compared with comparative example 1, the all-vanadium flow battery of example 1 group dress is due to the addition of APSF, and the resistance of composite membrane is
Increase, therefore charging voltage is higher than comparative example 1, discharge voltage is lower than comparative example 1.
Battery prepared by embodiment 1-3 and comparative example 1 is all-vanadium flow battery, selection of the coulombic efficiency by film to vanadium ion
Property determine, high coulombic efficiency illustrates that the self discharge degree of battery is relatively low.Energy efficiency reflection is benefit of the battery to energy
With rate, equal to the product of coulombic efficiency and voltage efficiency.Although the voltage efficiency with higher of comparative example 1, coulombic efficiency ratio
Lower, self discharge degree is high, therefore energy transformation ratio is also relatively low.Therefore all-vanadium flow battery is not suitable for it.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of perfluorinated sulfonic acid composite membrane, includes the following steps:
(1) mixed solution of the polysulfone resin after perfluorosulfonic acid proton exchange film and ammoniated treatment is prepared；
(2) mixed solution of step (1) is contacted with substrate, is heat-treated twice, it is compound that the perfluorinated sulfonic acid is prepared
Film.
2. preparation method according to claim 1, which is characterized in that step (1) includes the following steps:
Polysulfone resin after perfluorosulfonic acid proton exchange film and ammoniated treatment is dissolved in organic solvent respectively, perfluor is prepared
Sulfonic acid solutions and ammonification polysulfones solution, the two is mixed, mixed solution is prepared.
3. preparation method according to claim 1 or 2, which is characterized in that step (1) includes the following steps:
Polysulfone resin after pretreated perfluorosulfonic acid proton exchange film and ammoniated treatment is dissolved in organic solvent respectively, is made
It is standby to obtain perfluorinated sulfonic acid solution and ammonification polysulfones solution, the two is mixed, through 1~3h of magnetic agitation, 20~40min of ultrasonic disperse
4~7h is stood at a temperature of 40~80 DEG C afterwards, mixed solution is prepared.
4. preparation method according to claim 1-3, which is characterized in that in step (1), the perfluorinated sulfonic acid matter
Proton exchange is selected from pretreated perfluorosulfonic acid proton exchange film, or selected from discarded perfluorosulfonic acid proton exchange film,
Either it is selected from pretreated discarded perfluorosulfonic acid proton exchange film；
Preferably, in step (1), the organic solvent is n,N-Dimethylformamide, n,N-Dimethylformamide, N, N- diformazan
At least one of yl acetamide, dimethyl sulfoxide or N-Methyl pyrrolidone.
5. preparation method according to claim 1-4, which is characterized in that in step (1), the perfluorinated sulfonic acid is molten
The weight concentration of perfluorosulfonic acid proton exchange film is 2~10wt% in liquid, poly- after ammoniated treatment in the ammonification polysulfones solution
2~15wt% of weight concentration of sulphone resin；
Preferably, in step (1), polysulfone resin in the mixed solution after perfluorosulfonic acid proton exchange film and ammoniated treatment
Weight ratio is (60~99.999): (0.001~40).
6. preparation method according to claim 1-5, which is characterized in that in step (2), by including but unlimited
In casting, dipping, silk-screen, inkjet printing, roller coating, spray painting, spraying, spin coating and/or vapor deposition mode by mixed solution with
Substrate contact；
Preferably, in step (2), the substrate is selected from glass, monocrystalline silicon, polytetrafluoroethylene (PTFE) (PTFE), poly terephthalic acid second
At least one of diol ester (PET), polyethylene naphthalate (PEN), polyimides (PI) etc..
7. preparation method according to claim 1-6, which is characterized in that the step (2) includes the following steps:
The mixed solution of step (1) is coated to substrate surface, first time heat treatment, cooling are carried out under the conditions of 40~80 DEG C
Afterwards, second is carried out under 100~170 DEG C of vacuum conditions to be heat-treated, the perfluorinated sulfonic acid composite membrane is prepared；
Preferably, the step (2) includes the following steps:
The mixed solution of step (1) is coated to substrate surface, in 40~80 DEG C of baking oven carry out for the first time heat treatment 8~
14h is transferred in vacuum drying oven after cooling, and second of 3~6h of heat treatment is carried out in 100~170 DEG C of vacuum drying ovens, is prepared into
To the perfluorinated sulfonic acid composite membrane；
Preferably, the vacuum degree of the vacuum drying oven is 0.01-0.1MPa, for example, 0.08MPa.
8. a kind of perfluorinated sulfonic acid composite membrane, the composite membrane is prepared by the described in any item methods of claim 1-7
's；
Preferably, the perfluorinated sulfonic acid composite membrane with a thickness of 50~150 μm.
9. the purposes of perfluorinated sulfonic acid composite membrane according to any one of claims 8, is used for all-vanadium flow battery.
10. a kind of all-vanadium flow battery, the battery includes perfluorinated sulfonic acid composite membrane according to any one of claims 8.
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