CN108878937A - A kind of preparation method of Nafion/FCB composite diaphragm - Google Patents
A kind of preparation method of Nafion/FCB composite diaphragm Download PDFInfo
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- CN108878937A CN108878937A CN201810633855.6A CN201810633855A CN108878937A CN 108878937 A CN108878937 A CN 108878937A CN 201810633855 A CN201810633855 A CN 201810633855A CN 108878937 A CN108878937 A CN 108878937A
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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
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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
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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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
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to vanadium redox battery (vanadium cell) diaphragm fields, specifically a kind of preparation method of Nafion/FCB composite diaphragm, the problems such as solving that diaphragm existing in the prior art resistance vanadium performance is poor, proton conductivity is poor, stability is poor and is expensive.Functionalized carbon tube (FCB) is prepared using diazonium reactant salt using carbon material as raw material, it is obstructed into medium as the conduction of internal proton and vanadium ion, prepares Nafion/FCB composite diaphragm using film build methods such as substep curtain coating, pasting, impregnations using Nafion as matrix.Composite diaphragm prepared by the present invention has many advantages, such as good resistance vanadium performance, mechanically and chemically stability, proton-conducting and the superior battery performance of single VRB battery.The present invention breaks through traditional cation exchange membrane concept, introduces medium of the functionalized carbon tube as proton conducting, and the preparation for vanadium cell commercialization diaphragm provides new method.
Description
Technical field：
It is specifically a kind of the present invention relates to diaphragm field used in vanadium redox battery (vanadium cell or VRB)
Novel perfluoro sulfonate resin (Nafion)/functionalized carbon tube (FCB) composite diaphragm suitable for vanadium redox battery
Preparation method.
Figure viewed from behind technology：
Vanadium cell is a kind of most potential extensive energy storage electrochemical techniques, can be used for new cleaning fuel
(such as：Wind energy, solar power generation etc.) or the matched energy storage of power grid and release, realize the effective use of the energy.But mesh
Preceding diaphragm material restricts the commercialized development of vanadium cell because of its vanadium ion infiltration height.A kind of good diaphragm material should have good
The features such as proton conductivity well, mechanically and chemically stability, low vanadium ion infiltration, there are no vanadium cell commercializations to use at this stage
Diaphragm material, the diaphragm material that domestic and international vanadium cell demonstration engineering mainly uses for DuPont Corporation Nafion series
Film (Nafion membrane is perfluorinated sulfonic acid cationoid exchange membrane), but Nafion has vanadium ion infiltration greatly, self-discharge of battery is existing
As the disadvantages of serious, its application in vanadium cell industrialized development is restricted.
Lot of domestic and foreign mechanism is also modified research to Nafion diaphragm, although certain performances of enhancing Nafion membrane,
But its proton conductivity is affected, vanadium ion infiltration is still very high, still restricts the commercialization process of vanadium cell.In addition,
The disadvantages of these modifying process have complex process, and raw material is not easy to obtain, and additive is reunited.
Summary of the invention:
For overcome the deficiencies in the prior art, the constraint for breaking through conventional membrane, it is suitable that the purpose of the present invention is to provide one kind
The preparation method of novel Nafion/FCB composite diaphragm for vanadium cell solves diaphragm ion selection existing in the prior art
Property it is poor, proton conductivity is low, resistance vanadium performance is poor, the problems such as stability is poor and expensive.Using this method can get vanadium from
Son permeates the Nafion/FCB composite diaphragm well below Nafion membrane, with ion selectivity is good, proton conductivity is high, machine
Tool and chemical stability is strong and single vanadium cell in it is functional the advantages that.
Technical scheme is as follows：
A kind of preparation method of Nafion/FCB composite diaphragm, includes the following steps and process conditions：
(1) carbon material of drying process is dissolved in deionized water, being made into mass percent under ultrasound, stirring state is
1.5~12% carbon material solution；
(2) carbon material solution obtained in step (1) is ultrasonically treated, removes bubble and impurity, proton conduction official is added
Carrier can be rolled into a ball, the solution that proton conduction functional group's carrier quality percentage is 0.3~6% is made into, stirs 2~6h；
(3) solution obtained in step (2) is added an acid to, is vigorously stirred to form mixed solution；
(4) mixed solution in heating stepses (3), control temperature range are 20~95 DEG C, and sodium nitrite is then added, matches
The solution that sodium nitrite mass percent processed is 0.01~15%, control temperature range are 10~75 DEG C, react 3~9h；
(5) membrane filtration step (4) resulting solution is utilized；
(6) sulfuric acid for being successively 0.5M~1.0M with the ammonium sulfate solution of molar concentration 0.4M~1.5M, molar concentration
And deionized water, resulting solid matter is filtered to step (5) and is cleaned repeatedly；
(7) step (6) products obtained therefrom is freeze-dried, control temperature range is -120~-5 DEG C and obtains functionalized carbon tube
FCB；
(8) preparation method of Nafion solution：Dry Nafion diaphragm is dissolved in high boiling organic solvent, mass body
Product is than being Nafion：High boiling organic solvent=1/50~1/10g/mL is stirred to react 0.5 under 100~160 DEG C of constant temperatures
~6h；
(9) FCB obtained after step (7) freeze-drying is added after step (8) are reacted in gained Nafion solution, through stirring
It mixes and is ultrasonically treated, be made into the Nafion/FCB mixed solution of FCB mass percent 0.5~20%；
(10) Nafion/FCB mixed solution obtained by step (9) is added in channeled glass plate, then uses solution-casting method
Film forming impregnates to obtain Nafion/FCB composite diaphragm through deionized water after circulation heating is dried.
In the step (1), carbon material is one of conductive carbon black XC-72, BP 2000, EC 300, EC 600.
In the step (2), proton conduct functional group's carrier be p-aminobenzene sulfonic acid, p-aminobenzoic acid, p-phenylenediamine,
One of tetrabromoaniline, p-aminophenyl boric acid, p-aminophenyl phosphonic acids.
In the step (3), acid is one of hydrochloric acid, sulfuric acid, formic acid, acetic acid.
In the step (3), it is 1/60~1/6 that acid, which is added, and accounts for liquor capacity ratio obtained in step (2).
In the step (8), mixing speed is 500~1000r/min.
In the step (8), high boiling organic solvent is n,N-Dimethylformamide, dimethyl sulfoxide, N, N- dimethyl
One of acetamide, tetrahydrofuran, N-Methyl pyrrolidone.
In the step (9), FCB is added into Nafion solution, mixing speed is 500~1200r/min, ultrasonic treatment
Time is 40~80min.
In the step (10), circulation when solution-casting method forms a film, which heats up, to be dried, and the first step is 25~140 DEG C,
Drying time is 1~2h；Second step be 140~160 DEG C, drying time be 10~for 24 hours；Third step is 160~180 DEG C, dry
Time is 3~6h, this three steps temperature gradually rises；Later, it circuits sequentially.
In the step (10), soaking time is 16~32h.
Design philosophy of the invention is：
Functionalized carbon tube (FCB) has good proton conduction property and excellent hydrophilicity, fills with other diaphragms
Material is compared, it has many advantages, such as to prepare low raw-material cost, rich reserves and environmentally protective, and the present invention utilizes diazonium reactant salt
Carbon dust is handled, is grafted a large amount of proton exchange groups on the surface thereof, and then improves its hydrophily, dispersibility and ion selection
Property.The present invention prepares Nafion/FCB composite diaphragm by solution-casting method, there is good proton-conducting, extremely low vanadium ion
Permeance property and superior vanadium cell performance, this method for preparing composite diaphragm be expected to become a kind of vanadium cell commercialization with every
The preparation method of film.
Compared with prior art, the present invention has the advantages that following significant and beneficial effect：
1. the FCB that the present invention utilizes and traditional packing material are (such as：SiO2,GO,TiO2,WO3, CNT) and it compares, the original of FCB
Material storage is abundant and at low cost.Since matrix skeleton Nafion and FCB are effectively connected to together, compound membrane swelling entire in this way
Property reduce.Simultaneously as vanadium ion infiltration lane size becomes smaller or number of active lanes tails off, the infiltration of vanadium ion can be effectively reduced
Thoroughly, and then reduce self-discharge phenomenon, improve the efficiency of battery.
2. Nafion/FCB composite diaphragm prepared by the present invention effectively improves the mechanical performance and chemical stability of diaphragm,
And then improve stability of the composite diaphragm in vanadium cell.Due to the addition of FCB, can be improved between packing material and matrix skeleton
Interaction, promotes the mechanical stability of diaphragm, to improve its cyclical stability in the battery.
3. composite diaphragm prepared by the present invention obstructs medium using FCB material as proton conducting carrier and vanadium ion,
The oxygen-containing functional group of this kind of functional carbon material, to electrochemical catalysis activity, can be improved battery efficiency to vanadium ion electricity.
This kind of internal resistance is lower simultaneously, can reduce the ohmic polarization of cell operation, greatly improves battery operation current density.
The cost of the meeting same power density pile of much lower in this way, promotes the development of vanadium cell industrialization.
4. whole preparation process device therefor of the present invention has, cheap, cost of material is low, operation is convenient and environmentally friendly etc.
Industrial functionization feature facilitates the development for promoting vanadium cell commercialization diaphragm material and the business metaplasia for promoting vanadium cell
It produces.
In short, the present invention utilizes the Nafion/FCB composite diaphragm of solution-casting method preparation.This kind of composite diaphragm has good
Good proton-conducting, the infiltration of lower vanadium ion, good chemical stability and the capacity retention ratio in single vanadium cell
High, the high-efficient advantages such as low with self-discharge rate.The resistance of composite membrane is effectively reduced using FCB, while improving the matter of composite membrane
Sub- conductivity.FCB can effectively change ion conduction channel size inside diaphragm simultaneously, reduce vanadium ion infiltration, reduce vanadium
Self-discharge of battery problem is expected to prepare diaphragm material used in suitable vanadium cell industrialization using this preparation method.
Detailed description of the invention：
Fig. 1 is equipped with the vanadium cell power density comparison diagram of Nafion 212 and Nafion/FCB composite diaphragm.
Fig. 2 is equipped with the vanadium cell volumetric properties comparison diagram of Nafion 212 and Nafion/FCB composite diaphragm.
Fig. 3 is equipped with the vanadium cell efficiency chart of Nafion/FCB composite diaphragm.
Specific embodiment：
In the specific implementation process, the present invention prepares functionalized carbon tube using diazonium reactant salt using carbon material as raw material
(FCB), it is obstructed into medium as the conduction of internal proton and vanadium ion, while is using perfluorinated sulfonic acid class macromolecule (Nafion)
Matrix skeleton prepares Nafion solution using heating dissolution method.Using Nafion as matrix, FCB is added in Nafion solution,
Nafion/FCB composite diaphragm, Nafion/FCB are prepared using film build methods such as substep dispersion, solution blending and solution casting
Composite diaphragm is with a thickness of 15~75 μm.In the composite diaphragm, FCB content is 0.05~15wt% (preferably 6~12wt%).Institute
Obtaining composite diaphragm, FCB is uniformly dispersed, without dissolution phenomenon in appearance, while having preferable flexibility and mechanical performance.The present invention
Preparation method have it is simple and easy, low in cost, be easy to industrialization production and advantages of environment protection, can widely apply
In vanadium redox battery industrialization field.
The present invention is described further below with reference to embodiment and attached drawing.
Embodiment 1
In the present embodiment, the preparation method of Nafion/FCB composite diaphragm, specific step is as follows：
1, prepared by functional carbon material (FCB):By 2.0g carbon material (conductive carbon black XC-72) at 80 DEG C at vacuum drying
Reason is added in the flask for being placed with 280mL deionized water after 3 hours, ultrasonic 40min, stirs 3h.Then 2g functional group load is weighed
Body material is (such as：P-aminobenzene sulfonic acid or p-aminobenzoic acid etc.), it then stirs 2h and 1.5mL hydrochloric acid is added.Above-mentioned solution is existed
2.5h is heated in 50 DEG C of water-baths.It weighs 1g sodium nitrite to be added in above-mentioned solution, in 50 DEG C of water-bath 1.5h.It is taken out with decompression
Filter, ammonium sulfate solution, the molar concentration for recycling molar concentration 1.0M are 0.5M~1.0M sulfuric acid and deionized water, to institute
The solid matter (FCB on filtering filter membrane) obtained is cleaned, and is then freeze-dried under the conditions of -50 DEG C, is obtained FCB.
2, the preparation of Nafion：212 film of Nafion for taking 2.2g dry, shreds, is added to the N of 50mL, N- dimethyl formyl
In amine aqueous solution, under 120 DEG C of heating conditions, Nafion solution is made in stir process 8h, mixing speed 800r/min.
3, the preparation method of Nafion/FCB composite diaphragm, includes the following steps：
(1) 100mg step 1 gained FCB is added in step 2 gained Nafion solution, it is molten obtains Nafion/FCB mixing
Liquid.Wherein, the FCB content of Nafion/FCB mixed solution is 4.35wt%.
(2) it is 800r/min stirring 2h with mixing speed by mixed solution obtained by step (1) and is ultrasonically treated 50min, obtains
To finely dispersed Nafion/FCB mixed solution.
(3) mixed solution obtained by step (2) is added in channeled glass plate (horizontal positioned).Using casting membrane formation process at
Film, under the conditions of 60 DEG C dry 1.5h, heat up after drying process in 140 DEG C of dry 15h, in the circulation of 160 DEG C of dry 5h, through going
Ionized water impregnates for 24 hours, obtains Nafion/FCB composite diaphragm.
Wherein, recycling the effect that heating is dried is：(1) 60 DEG C of drying purpose is to make FCB in organic solvent
Disperse more evenly, so that FCB evenly dispersed can be embedded in Nafion macromolecular scaffold in film forming procedure；(2)140℃
Drying is for the crystal form for forming it into stable homogeneous dry under Nafion glass transition temperature；(3) 160 DEG C of drying purposes make organic
Solvent volatilizees away completely, further ensures that the uniformity of composite membrane.
In the present embodiment, for the Nafion/FCB composite diaphragm of acquisition with a thickness of 51 μm, composite diaphragm is homogeneous, fine and close,
No FCB dissolves out phenomenon, while having preferable suppleness and mechanical performance.Composite diaphragm is measured at room temperature in whole vanadium oxide reduction
Internal resistance in flow battery is 0.49 Ω cm2, 212 film of Nafion is 0.58 Ω cm under equal conditions2。
The correlated performance data of the present embodiment is as follows：
As shown in Figure 1, the vanadium cell equipped with ratio Nafion/FCB composite diaphragm is due to Nafion/FCB ratio at room temperature
Nafion212 membrane surface resistance is small, so having small polarization, therefore power density with higher.As shown in Fig. 2, being equipped with
The vanadium cell capacity retention ratio of Nafion/FCB composite diaphragm is higher than the vanadium cell capacity retention ratio equipped with 212 film of Nafion, table
Bright FCB addition can effectively improve composite diaphragm to the barrier action of vanadium ion, and battery self discharge rate is low.As shown in figure 3, being equipped with
The single vanadium cell of Nafion/FCB composite diaphragm has very high coulombic efficiency, voltage efficiency and energy efficiency, is suitble to storing up
Can field large-scale application, while passing through multiple charge and discharge cycles, coulombic efficiency, voltage efficiency and energy efficiency are without obviously declining
Subtract.Illustrate that the composite diaphragm can especially be stablized in the pentavalent vanadium ion sulfuric acid solution of strong oxidizing property in electrolyte of vanadium redox battery to deposit
There is good chemical cycle and prolonged cell stability.This Nafion/FCB composite diaphragm for implementing to prepare from example is suitble to
Vanadium cell industrial application.
Embodiment 2：
Difference from Example 1 is：
It weighs 50mg step 1 gained FCB to be added in step 2 gained Nafion solution, using remaining step system in embodiment 1
Standby Nafion/FCB composite diaphragm.Wherein, the FCB content of Nafion/FCB mixed solution is 2.22wt%.
In the present embodiment, for the Nafion/FCB composite diaphragm of acquisition with a thickness of 50 μm, composite diaphragm is homogeneous, have compared with
Strong toughness, no FCB dissolve out phenomenon.Measuring internal resistance of the diaphragm in vanadium redox battery at room temperature is 0.62 Ω
cm2, 212 film of Nafion is 0.58 Ω cm under equal conditions2.But the film, since FCB addition content is very few, vanadium ion infiltration is big,
With self-discharge phenomenon similar with 212 film of Nafion, be not suitable for vanadium cell practical application.
Embodiment 3
Difference from Example 1 is：
It weighs 250mg step 1 gained FCB to be added in step 2 gained Nafion solution, using remaining step in embodiment 1
Prepare Nafion/FCB composite diaphragm.Wherein, the FCB content of Nafion/FCB mixed solution is 10.2wt%.
In the present embodiment, for the Nafion/FCB composite diaphragm of acquisition with a thickness of 53 μm, composite diaphragm is homogeneous, have compared with
Strong toughness, but since FCB addition content is excessive, surface has FCB to dissolve out phenomenon.Due to the good electron conduction of FCB, simultaneously
Ratio FCB runs through film surface and inside, forms the electron channel of connection, therefore the diaphragm has short circuit phenomenon in the battery,
Internal resistance of the composite diaphragm in vanadium redox battery can not be measured at room temperature.Therefore, the ratio composite diaphragm without
Method practical application in vanadium cell.
Embodiment the result shows that, the present invention designs a proton and conducts high functional carbon material, and is added to it
In Nafion membrane, its selectivity to proton and vanadium ion is improved, this kind of composite diaphragm has good proton conductivity, well
Resistance vanadium performance, mechanically and chemically stability, and the advantages that single VRB battery superior battery performance.The present invention, which is broken through, to be passed
System cation-exchange membrane concept introduces medium of the functionalized carbon tube as proton conducting, is vanadium redox battery quotient
The preparation of industry diaphragm provides new method.This diaphragm preparation method, it will provided for vanadium cell industrialized development with diaphragm
A kind of new method is expected to become the preparation method of vanadium cell commercialization diaphragm.
Claims (10)
1. a kind of preparation method of Nafion/FCB composite diaphragm, which is characterized in that include the following steps and process conditions：
(1) carbon material of drying process is dissolved in deionized water, ultrasound, be made under stirring state mass percent be 1.5~
12% carbon material solution；
(2) carbon material solution obtained in step (1) is ultrasonically treated, removes bubble and impurity, proton is added and conducts functional group
Carrier is made into the solution that proton conduction functional group's carrier quality percentage is 0.3~6%, stirs 2~6h；
(3) solution obtained in step (2) is added an acid to, is vigorously stirred to form mixed solution；
(4) mixed solution in heating stepses (3), control temperature range are 20~95 DEG C, and sodium nitrite is then added, and are prepared sub-
The solution that sodium nitrate mass percent is 0.01~15%, control temperature range are 10~75 DEG C, react 3~9h；
(5) membrane filtration step (4) resulting solution is utilized；
(6) it the sulfuric acid for being successively 0.5M~1.0M with the ammonium sulfate solution of molar concentration 0.4M~1.5M, molar concentration and goes
Ionized water filters resulting solid matter to step (5) and is cleaned repeatedly；
(7) step (6) products obtained therefrom is freeze-dried, control temperature range is -120~-5 DEG C and obtains functionalized carbon tube FCB；
(8) preparation method of Nafion solution：Dry Nafion diaphragm is dissolved in high boiling organic solvent, mass volume ratio
For Nafion：High boiling organic solvent=1/50~1/10g/mL, it is stirred to react 0.5 under 100~160 DEG C of constant temperatures~
6h；
(9) FCB that obtains after step (7) freeze-drying is added after step (8) reaction in gained Nafion solution, it is agitated simultaneously
Ultrasonic treatment, is made into the Nafion/FCB mixed solution of FCB mass percent 0.5~20%；
(10) Nafion/FCB mixed solution obtained by step (9) is added in channeled glass plate, then is formed a film using solution-casting method,
After circulation heating is dried, impregnate to obtain Nafion/FCB composite diaphragm through deionized water.
2. the preparation method of Nafion/FCB composite diaphragm according to claim 1, which is characterized in that the step (1)
In, carbon material is one of conductive carbon black XC-72, BP 2000, EC 300, EC 600.
3. the preparation method of Nafion/FCB composite diaphragm according to claim 1, which is characterized in that the step (2)
In, it is p-aminobenzene sulfonic acid, p-aminobenzoic acid, p-phenylenediamine, tetrabromoaniline, p-aminophenyl boron that proton, which conducts functional group's carrier,
One of acid, p-aminophenyl phosphonic acids.
4. the preparation method of Nafion/FCB composite diaphragm according to claim 1, which is characterized in that the step (3)
In, acid is one of hydrochloric acid, sulfuric acid, formic acid, acetic acid.
5. the preparation method of Nafion/FCB composite diaphragm according to claim 1, which is characterized in that the step (3)
In, it is 1/60~1/6 that acid, which is added, and accounts for liquor capacity ratio obtained in step (2).
6. the preparation method of Nafion/FCB composite diaphragm according to claim 1, which is characterized in that the step (8)
In, mixing speed is 500~1000r/min.
7. the preparation method of Nafion/FCB composite diaphragm according to claim 1, which is characterized in that the step (8)
In, high boiling organic solvent is n,N-Dimethylformamide, dimethyl sulfoxide, n,N-dimethylacetamide, tetrahydrofuran, N- first
One of base pyrrolidones.
8. the preparation method of Nafion/FCB composite diaphragm according to claim 1, which is characterized in that the step (9)
In, FCB is added into Nafion solution, mixing speed is 500~1200r/min, and sonication treatment time is 40~80min.
9. the preparation method of Nafion/FCB composite diaphragm according to claim 1, which is characterized in that the step (10)
In, circulation when solution-casting method forms a film, which heats up, to be dried, and the first step is 25~140 DEG C, and drying time is 1~2h；Second
Step be 140~160 DEG C, drying time be 10~for 24 hours；Third step is 160~180 DEG C, and drying time is 3~6h, this three steps temperature
Degree gradually rises；Later, it circuits sequentially.
10. the preparation method of Nafion/FCB composite diaphragm according to claim 1, which is characterized in that the step
(10) in, soaking time is 16~32h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113471464A (en) * | 2021-05-19 | 2021-10-01 | 深圳先进技术研究院 | Material for battery diaphragm, material preparation method and battery diaphragm |
| CN114220983A (en) * | 2021-12-15 | 2022-03-22 | 南京工业大学 | Modified membrane based on hollow carbon spheres and preparation method and application thereof |
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| CN113471464A (en) * | 2021-05-19 | 2021-10-01 | 深圳先进技术研究院 | Material for battery diaphragm, material preparation method and battery diaphragm |
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| CN114220983A (en) * | 2021-12-15 | 2022-03-22 | 南京工业大学 | Modified membrane based on hollow carbon spheres and preparation method and application thereof |
| CN114220983B (en) * | 2021-12-15 | 2024-01-30 | 南京工业大学 | Modified membrane based on hollow carbon spheres and preparation method and application thereof |
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