CN105140543A - Flow cell ion exchange membrane assembly, preparing method of flow cell ion exchange membrane assembly and flow cell comprising flow cell ion exchange membrane assembly - Google Patents
Flow cell ion exchange membrane assembly, preparing method of flow cell ion exchange membrane assembly and flow cell comprising flow cell ion exchange membrane assembly Download PDFInfo
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- CN105140543A CN105140543A CN201510543135.7A CN201510543135A CN105140543A CN 105140543 A CN105140543 A CN 105140543A CN 201510543135 A CN201510543135 A CN 201510543135A CN 105140543 A CN105140543 A CN 105140543A
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0276—Sealing means characterised by their form
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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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- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0239—Organic resins; Organic polymers
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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
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Abstract
The invention discloses a flow cell ion exchange membrane assembly, a preparing method of the flow cell ion exchange membrane assembly and a flow cell comprising the flow cell ion exchange membrane assembly. The flow cell ion exchange membrane assembly comprises a porous membrane, an iron exchange area coating arranged in the middle area of the porous membrane, and a sealing area coating arranged in the area, outside the ion exchange area coating, of the porous membrane. The preparing method includes the following steps that firstly, the porous membrane serves as the base material, the middle area of the porous membrane is coated with the ion exchange area coating; secondly, the area, outside the ion exchange area coating, of the porous membrane is coated with the sealing area coating. By means of the technical scheme, due to the existence of a sealing area, sealing rings or sealing gaskets do not need to be embedded or added to liquid flow frames on the two sides of the flow cell ion exchange membrane assembly when a cell stack is assembled, the processing cost and the assembling difficulty of cells are lowered, and meanwhile the problem of the sealing failure caused by water absorption swelling of the iron exchange membrane in conventional design can also be solved.
Description
Technical field
The present invention relates to flow battery technology field, be specifically related to a kind of flow battery ion-exchange membrane module, its preparation method and comprise its flow battery.
Background technology
Flow battery is a class model electrochemical energy storage system, compared to other energy storage technologies, the advantages such as flow battery has that power is large, capacity is large, energy conversion efficiency is high, long service life, fail safe are high, environmental protection, are having broad application prospects with the field such as photovoltaic generation and supporting large-scale energy storage system, intelligent grid peak regulation, communication base station and the distributed power source of wind power generation.Vanadium redox battery is the one in flow battery, and it is using the vanadium ion electrolyte of different valence state as the both positive and negative polarity active material of battery, just very V
4+/ V
5+electricity is right, and negative pole is V
2+/ V
3+electricity is right.The both positive and negative polarity of battery is separated by amberplex, and both positive and negative polarity electrolyte is stored in two outside fluid reservoirs respectively, to be pumped in battery plus-negative plate room by electrolyte complete electrochemical reaction by pump, returns in fluid reservoir to form closed circulation liquid and flow back to road.
As shown in Figure 1, wherein 10 ' is bipolar plates to existing flow battery pile structure, and 20 ' is liquid flow frame, 30 ' is porous electrode, 40 ' is amberplex, and porous electrode 30 ' is nested in the middle hollow out position of liquid flow frame 20 ', constantly repeats to stack together by order shown in figure.Contact-making surface in order to avoid electrolyte from amberplex 40 ' with liquid flow frame 20 ' oozes out, and usually needs the upper embedding sealing circle (linear sealing) of the liquid flow frame 20 ' in amberplex 40 ' both sides or add gasket seal (face sealing) to realize sealing.But, battery pile is in actual motion, the moisture of amberplex often in Electolyte-absorptive and swelling set occurs, make liquid flow frame and ion-exchange intermembranous being easy to that seal failure occur, cause battery pile leakage, the mechanical strength of swelling rear amberplex declines on the other hand, very easily mechanical damage occurs, also easily cause cell sealing to lose efficacy under sealing ring or the long-term pressurized state of gasket seal.
Summary of the invention
The present invention is directed to the problems referred to above, provide a kind of flow battery ion-exchange membrane module, its preparation method and comprise its flow battery, need on the liquid flow frame of amberplex both sides embedding sealing circle to solve in prior art or add the seal failure problem that gasket seal carries out sealing and amberplex swelling set brings.
To achieve these goals, according to an aspect of the present invention, a kind of flow battery ion-exchange membrane module is provided.This flow battery ion-exchange membrane module comprises: perforated membrane; Ion-exchange area coating, is arranged on the zone line of perforated membrane; Seal area coating, is arranged on the region outside the coating of perforated membrane deionization exchange area.
Further, the integrated perforated membrane of perforated membrane.
Further, perforated membrane is organic porous films.
Further, perforated membrane is the perforated membrane of polytetrafluoroethylene, Kynoar, polysulfones, polyimides, polypropylene, polyethylene, PAEK or polyether sulfone material.
Further, perforated membrane has upper surface, lower surface and multiple perfoliate hole, ion-exchange area coating be in the hole of the zone line of perforated membrane, upper surface and/or lower surface Coating Ions exchanger resin formed; Seal area coating be region outside the coating of perforated membrane deionization exchange area hole in, upper surface and/or lower surface coating sealing material formed.
Further, ion exchange resin is cation exchange resin or anion exchange resin.
Further, ion exchange resin contains inorganic nano-particle.
Further, inorganic nano-particle comprises nano silicon, nano titanium oxide, carbon nano-tube and derivative thereof or Graphene and derivative thereof.
Further, sealing material is encapsulant resin or anti-corrosive rubber.
Further, the thickness of ion-exchange area coating and the thickness of seal area coating identical or different.
According to another aspect of the present invention, a kind of flow battery is provided.This flow battery comprises flow battery ion-exchange membrane module, and flow battery ion-exchange membrane module is as any one flow battery ion-exchange membrane module above-mentioned.
According to another aspect of the present invention, a kind of preparation method of above-mentioned flow battery ion-exchange membrane module is provided.This preparation method comprises the following steps: S1, using perforated membrane as basis material, in the zone line Coating Ions exchange area coating of perforated membrane; And S2, coating seal area, the region coating outside the coating of perforated membrane deionization exchange area.
Further, the integrated organic porous films of perforated membrane.
Further, S1 specifically comprises: be dissolved in by ion exchange resin in the good solvent of ion exchange resin and form the first polymer solution, first polymer solution is coated to the zone line of perforated membrane, removes the good solvent of ion exchange resin, make ion exchange resin film-forming.
Further, further containing the inorganic nano ion of 0.01 ~ 25wt% in the first polymer solution, inorganic nano-particle comprises nano silicon, nano titanium oxide, carbon nano-tube and derivative thereof or Graphene and derivative thereof.
Further, the surfactant further containing 0.01 ~ 5wt% in the first polymer solution.
Further, S2 specifically comprises: encapsulant resin be dissolved in the good solvent of encapsulant resin and form the second polymer solution, second polymer solution is coated to the region outside the coating of perforated membrane deionization exchange area, removes the good solvent of encapsulant resin, make encapsulant resin film-forming; Or carry out after anti-corrosive rubber is mixed with auxiliary agent mixingly obtaining mixing anti-corrosive rubber, mixing anti-corrosive rubber is dissolved in the good solvent of mixing anti-corrosive rubber and makes rubber cement, rubber cement is coated to the region outside the coating of perforated membrane deionization exchange area, remove the good solvent of mixing anti-corrosive rubber, make mixing anti-corrosive rubber film-forming.
Further, auxiliary agent is crosslinking agent.
Further, S1 and/or S2 is repeated more than twice or twice.
Further, the pre-treatment step to perforated membrane is comprised before S1: adopt ethanol or isopropyl alcohol to soak perforated membrane.
Apply technical scheme of the present invention, by Coating Ions exchange area coating and coating formation Coating Ions exchange area, seal area and seal area on perforated membrane, because the existence of seal area, this flow battery ion-exchange membrane module cell stack timing not need on the liquid flow frame of ion-exchange membrane module both sides embedding sealing circle or add gasket seal, reduce battery pile processing cost and assembly difficulty, also can avoid the seal failure problem that conventional design intermediate ion exchange membrane water absorption and swelling causes simultaneously.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the structural representation of liquid stream battery stack in prior art; And
Fig. 2 shows the structural representation of ion-exchange membrane module according to an embodiment of the invention.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
For needing embedding sealing circle or interpolation gasket seal on the liquid flow frame of amberplex both sides to carry out the seal failure problem sealed and amberplex swelling set brings in prior art, the present invention proposes following technical scheme.
A kind of flow battery ion-exchange membrane module is typically embodiment there is provided according to one of the present invention.As shown in Figure 1, this flow battery ion-exchange membrane module comprises perforated membrane, is arranged on the ion-exchange area coating 41 of the zone line of perforated membrane and is arranged on the seal area coating 42 in the region outside perforated membrane deionization exchange area coating 41.Apply technical scheme of the present invention, by Coating Ions exchange area coating and coating formation Coating Ions exchange area, seal area and seal area on perforated membrane, because the existence of seal area, this flow battery ion-exchange membrane module cell stack timing not need on the liquid flow frame of ion-exchange membrane module both sides embedding sealing circle or add gasket seal, reduce battery pile processing cost and assembly difficulty, also can avoid the seal failure problem that conventional design intermediate ion exchange membrane water absorption and swelling causes simultaneously.
In the present invention, the shape and size of ion-exchange area and seal area, according to pile actual design, can adopt any shape and size.
Preferably, the integrated perforated membrane of perforated membrane, can reduce battery pile processing cost and assembly difficulty, improves useful life and the stability of this flow battery ion-exchange membrane module simultaneously.
According to a kind of typical execution mode of the present invention, perforated membrane is organic porous films, the perforated membrane of the materials such as such as polytetrafluoroethylene, Kynoar, polysulfones, polyimides, polypropylene, polyethylene, PAEK or polyether sulfone.The integrated ion-exchange membrane module of this perforated membrane provides support frame, amberlite district coating and seal coating are combined as a whole, this perforated membrane skeleton also plays mechanical humidification simultaneously, can reduce the consumption of coating resin, and then reduces production cost.This perforated membrane has upper surface, lower surface and multiple perfoliate hole, as shown in Figure 2, ion-exchange area coating 41 be in the hole of the zone line of perforated membrane, upper surface and/or lower surface Coating Ions exchanger resin formed; Seal area coating 42 be region outside perforated membrane deionization exchange area coating 41 hole in, upper surface and/or lower surface coating sealing material formed, namely ion-exchange area coating 41 and seal area coating 42 can be prepared into coated on both sides according to actual needs or one side coating, as long as be evenly distributed at porous film surface and run through Porous-Organic film thickness direction.
According to a kind of typical execution mode of the present invention, ion exchange resin is cation exchange resin or anion exchange resin.Preferably, ion exchange resin contains inorganic nano-particle, this inorganic nano-particle can be the inorganic nano-particle or functional inorganic nano particle, such as nano silicon, nano titanium oxide, carbon nano-tube and derivative thereof or Graphene and derivative etc. thereof that can change to flow battery amberplex assembly property.
Preferably, sealing material is encapsulant resin or anti-corrosive rubber, encapsulant resin alleged in the present invention refers to that softness has the macromolecular material of compliance, such as polytetrafluoroethylene, Kynoar etc., anti-corrosive rubber refers to the high elastic rubber of resistance to chemical attack (especially acidproof), such as the corrosion resistant material such as fluorubber, ethylene-propylene rubber.
According to a kind of typical execution mode of the present invention, the thickness of ion-exchange area coating 41 and the thickness of seal area coating 42 identical or different, can set according to actual needs.
According to a kind of typical execution mode of the present invention, provide a kind of flow battery.This flow battery comprises any one flow battery ion-exchange membrane module above-mentioned.
According to a kind of typical execution mode of the present invention, provide a kind of preparation method of above-mentioned flow battery ion-exchange membrane module.Do not have the step described in detail can be realized by ordinary skill in the art means in the present invention.This preparation method comprises the following steps: S1, using perforated membrane as basis material, in the zone line Coating Ions exchange area coating 41 of perforated membrane; And S2, coating seal area, the region coating 42 outside perforated membrane deionization exchange area coating 41.Apply technical scheme of the present invention, by Coating Ions exchange area coating and coating formation Coating Ions exchange area, seal area and seal area on perforated membrane, because the existence of seal area, this flow battery ion-exchange membrane module cell stack timing not need on the liquid flow frame of ion-exchange membrane module both sides embedding sealing circle or add gasket seal, reduce battery pile processing cost and assembly difficulty, also can avoid the seal failure problem that conventional design intermediate ion exchange membrane water absorption and swelling causes simultaneously.
In order to ensure not occur gap between ion-exchange area and seal area, both positive and negative polarity electrolyte is avoided to be interpenetrated the phenomenon causing battery drain by the perforated membrane of gap location, in actual mechanical process, can first Coating Ions exchange area coating, and then applying seal area coating, seal area coating slightly covers the border of ion-exchange area coating.
Coating alleged in the present invention can pass through spraying, brushing, blade coating, the realization of impregnating technique, and coating should be even.Ion-exchange area coating is relevant with the painting method used with the boundary Control of seal area coating, and such as spraying is the program control spray gun spraying path by spraying equipment, and dipping then needs the fixture by having mask functions to control.
Preferably, the integrated perforated membrane of perforated membrane, can reduce battery pile processing cost and assembly difficulty, improves useful life and the stability of this flow battery ion-exchange membrane module simultaneously.
According to a kind of typical execution mode of the present invention, S1 specifically comprises: be dissolved in by ion exchange resin in the good solvent of ion exchange resin and form the first polymer solution, first polymer solution is coated to the zone line of perforated membrane, remove the good solvent of ion exchange resin, make ion exchange resin film-forming.Wherein, make ion exchange resin film-forming can be under uniform temperature, pressure condition, make resin solidification after solvent flashing, concrete temperature, pressure condition can be determined according to the performance of institute's spent ion exchange resin own, such as make solvent evaporates at a lower temperature, then be elevated to higher temperature and make melting, cooling curing afterwards.First polymer solution also can directly commodity in use amberlite lipoprotein solution substitute.Usually require evenly, to ensure the quality of flow battery ion-exchange membrane module when the first polymer solution coating.
Above-mentioned ion exchange resin can be cation exchange resin can be also anion exchange resin, includes but not limited to Nafion (perfluorinated sulfonic acid), sulfonated polyether-ether-ketone, sulfonated polyether sulfone, sulfonated polyether ketone, sulfonated polyimide, quaternary polysulfones etc.Solvent for use is the good solvent of energy dissolved ions exchanger resin, as water, ethanol, isopropyl alcohol, ethylene glycol, dimethyl sulfoxide (DMSO) (DMSO), 1-METHYLPYRROLIDONE (NMP), N, N, one or more in-dimethyl formamide (DMF) equal solvent.
Preferably, further containing the inorganic nano ion of 0.01 ~ 25wt% in the first polymer solution, inorganic nano-particle comprises nano silicon, nano titanium oxide, carbon nano-tube and derivative thereof or Graphene and derivative thereof.By the vanadium ion barrier property adding raising ion-exchange area of inorganic nano-particle.In actual production process, first inorganic nano ion can be scattered in solvent and the ion exchange resin adding certain percentage obtains homodisperse solution, or directly inorganic nano uniform ion be scattered in commercial amberlite lipoprotein solution.Wherein, the dispersion of inorganic nano ion in amberlite lipoprotein solution can be the obtainable various method of ABC that those skilled in the art grasp in conjunction with it.
Preferably, the surfactant further containing 0.01 ~ 5wt% in the first polymer solution, increases amberlite lipoprotein solution to the wettability of organic porous films.Surfactant is as octylphenol polyethylene ethoxy ethanol (TritonX-100), dodecyl sodium sulfate, polysorbate60, Tween 80, TBAB etc.
According to a kind of typical execution mode of the present invention, S2 specifically comprises: encapsulant resin be dissolved in the good solvent of encapsulant resin and form the second polymer solution, second polymer solution is coated to the region outside perforated membrane deionization exchange area coating 41, remove the good solvent of encapsulant resin, make encapsulant resin film-forming; Or carry out after anti-corrosive rubber is mixed with auxiliary agent mixingly obtaining mixing anti-corrosive rubber, mixing anti-corrosive rubber is dissolved in the good solvent of mixing anti-corrosive rubber and makes rubber cement, rubber cement is coated to the region outside perforated membrane deionization exchange area coating 41, remove the good solvent of mixing anti-corrosive rubber, make mixing anti-corrosive rubber film-forming.According to a kind of typical execution mode of the present invention, auxiliary agent is crosslinking agent, and anti-corrosive rubber is crosslinking curing under the effect of crosslinking agent, is convenient to factorial praluction.The cross-linking process of above-mentioned anti-corrosive rubber can be that crosslinked or two steps of a step are cross-linked, and crosslinking agent can adopt Diamines vulcanizing agent, bisphenols vulcanizing agent or peroxide-based curing dose.
In above-mentioned sealing material and amberlite lipoprotein solution or rubber cement coating procedure, for accelerating impregnating speed, raise the efficiency, by perforated membrane preliminary treatment with increase polymer solution or rubber cement wettability, increase polymer solution or rubber cement pressure or reduce its viscosity and realize with the approach such as to improve liquidity.The preliminary treatment of organic porous films can adopt ethanol, isopropyl alcohol equal solvent to soak, and reduction polymer solution or cement viscosity can adopt and improve temperature, reduction solution concentration or add the methods such as diluent.
According to a kind of typical execution mode of the present invention, repeat S1 and/or S2 more than twice or twice, thus obtain the thickness wishing to obtain.In addition, required thickness requirement is reached by controlling the approach such as solution concentration, coating processes.
Beneficial effect of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Raw material: select that thickness is 50mm, the PTFE of aperture 0.1-0.3mm (polytetrafluoroethylene) perforated membrane is organic porous films matrix, the PTFE emulsion of 10wt% is encapsulant resin solution, Nafion (perfluorinated sulfonic acid) solution of 5wt% is amberlite lipoprotein solution, and adds the surfactant TritonX-100 (Triton X-100) of 0.5% in Nafion solution.
Implementation process: first PTFE perforated membrane is put into after isopropyl alcohol soaks 30min, take out nature and dry.Pretreated PTFE perforated membrane is sandwiched on fixture processed, PTFE emulsion is evenly brushed the upper and lower both sides of perforated membrane in position, seal area, then put into baking oven, heat treatment 30min desolvation at 120 DEG C, be warmed up to 300 DEG C of heat treatment 20min afterwards and make it solidification, take out after cooling.The PTFE perforated membrane having applied encapsulant is sandwiched in particular jig, the mode of brushing is adopted Nafion dissolution homogeneity to be coated on the upper and lower both sides of perforated membrane at position, ion-exchange area, then baking oven is put into, heat treatment 30min desolvation film forming at 140 DEG C, after cooling gained film is immersed in isopropanol solvent and remove TritonX-100, after naturally drying, namely obtain integrated film electrode assemblie.
Embodiment 2
Raw material: select that thickness is 30mm, the polyimide porous membrane of aperture 0.2-0.5mm is organic porous films matrix, fluorubber is sealing material, and sulfonated polyether-ether-ketone is ion exchange resin.
Implementation process: first add the crosslinking agent benzoyl peroxide of 2% in crude fluororubber, adopt double roll mill to carry out mixing, then elastomeric compound is dissolved in ethyl acetate, the Fluororubber paste of obtained 10%.Polyimide porous membrane is sandwiched on fixture, Fluororubber paste is evenly brushed the upper and lower both sides of perforated membrane in position, seal area, then at 160 DEG C, carry out one step cure, be warmed up to 250 DEG C afterwards and carry out post vulcanization, take out after cooling.The polyimide porous membrane having applied fluorubber encapsulant is sandwiched in particular jig, the mode of spraying is adopted Nafion dissolution homogeneity to be coated on the upper and lower both sides of perforated membrane at position, ion-exchange area, then baking oven is put into, at 140 DEG C, heat treatment 30min desolvation film forming, namely obtains integrated film electrode assemblie after cooling.
Embodiment 3
Raw material: select that thickness is 20mm, the PTFE perforated membrane of aperture 0.1-0.3mm is organic porous films matrix, the PTFE emulsion of 10wt% is encapsulant resin solution, the Nafion solution of 5wt% is amberlite lipoprotein solution, and graphene oxide is inorganic nano-particle additive.
Implementation process: first PTFE perforated membrane is put into after isopropyl alcohol soaks 30min, take out nature and dry.Pretreated PTFE perforated membrane is sandwiched on fixture, PTFE emulsion is evenly brushed the upper and lower both sides of perforated membrane in position, seal area, then put into baking oven, heat treatment 30min desolvation at 120 DEG C, be warmed up to 300 DEG C of heat treatment 20min afterwards and make it solidification, take out after cooling.Graphene oxide (Nafion: graphene oxide=50:1) is added in Nafion solution, the PTFE perforated membrane having applied encapsulant is sandwiched in particular jig, adopt the mode of brushing by the upper and lower both sides of the perforated membrane of Nafion/ graphene oxide mixed solution even application in position, ion-exchange area, then vacuum drying oven is put into, at 80 DEG C, process 24h desolvation film forming, after cooling, namely obtain integrated film electrode assemblie.
As can be seen from the above description, present invention achieves following technique effect:
(1) after flow battery adopts integrated ion-exchange membrane module, not need on the liquid flow frame of integrated ion-exchange membrane module both sides embedding sealing circle or add gasket seal, greatly reduce battery pile processing cost and assembly difficulty, also effectively can avoid the seal failure problem that conventional design intermediate ion exchange membrane water absorption and swelling causes simultaneously.
(2) only Coating Ions exchanger resin in the porous film surface and hole at ion-exchange area place, can effectively reduce barrier film cost, and then reduce battery pile cost.
(3) apply encapsulant resin in the organic porous films surface at seal area place and hole, the vanadium ion in both positive and negative polarity electrolyte can be avoided to be interpenetrated by the micropore of organic porous films.
(4) integrated ion-exchange membrane module is using organic porous films as support substrate, effectively can increase the mechanical strength of barrier film, extend its useful life.
(5) sealing material and ion exchange resin adopt solwution method to be coated on the relevant position of organic porous films, easy to prepare, and technique is simple, low for equipment requirements.
(6) sealing material and the ion exchange resin film-forming process on organic porous films is easy to realize, and thickness is easy to control.
(7) inorganic nano ion can be added in ion exchange resin, the resistance vanadium performance of barrier film can be strengthened, improve barrier film mechanical performance or other function is provided.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (20)
1. a flow battery ion-exchange membrane module, is characterized in that, comprising:
Perforated membrane;
Ion-exchange area coating (41), is arranged on the zone line of described perforated membrane;
Seal area coating (42), is arranged on the region of described perforated membrane except described ion-exchange area coating (41).
2. flow battery ion-exchange membrane module according to claim 1, is characterized in that, the integrated perforated membrane of described perforated membrane.
3. flow battery ion-exchange membrane module according to claim 1, is characterized in that, described perforated membrane is organic porous films.
4. flow battery ion-exchange membrane module according to claim 3, is characterized in that, described perforated membrane is the perforated membrane of polytetrafluoroethylene, Kynoar, polysulfones, polyimides, polypropylene, polyethylene, PAEK or polyether sulfone material.
5. flow battery ion-exchange membrane module according to claim 1, it is characterized in that, described perforated membrane has upper surface, lower surface and multiple perfoliate hole, described ion-exchange area coating (41) be in the described hole of the zone line of described perforated membrane, described upper surface and/or lower surface Coating Ions exchanger resin formed; Described seal area coating (42) be in the described hole in the region of described perforated membrane except described ion-exchange area coating (41), described upper surface and/or lower surface coating sealing material formed.
6. flow battery ion-exchange membrane module according to claim 5, is characterized in that, described ion exchange resin is cation exchange resin or anion exchange resin.
7. flow battery ion-exchange membrane module according to claim 5, it is characterized in that, described ion exchange resin contains inorganic nano-particle.
8. flow battery ion-exchange membrane module according to claim 7, is characterized in that, described inorganic nano-particle comprises nano silicon, nano titanium oxide, carbon nano-tube and derivative thereof or Graphene and derivative thereof.
9. flow battery ion-exchange membrane module according to claim 5, is characterized in that, described sealing material is encapsulant resin or anti-corrosive rubber.
10. flow battery ion-exchange membrane module according to claim 1, is characterized in that, the thickness of described ion-exchange area coating (41) and the thickness of described seal area coating (42) identical or different.
11. 1 kinds of flow batteries, comprise flow battery ion-exchange membrane module, it is characterized in that, described flow battery ion-exchange membrane module is the flow battery ion-exchange membrane module such as according to any one of claim 1 to 10.
The preparation method of 12. 1 kinds of flow battery ion-exchange membrane modules according to any one of claim 1 to 10, is characterized in that, comprise the following steps:
S1, using perforated membrane as basis material, in zone line Coating Ions exchange area coating (41) of described perforated membrane; And
S2, in region coating seal area coating (42) of described perforated membrane except described ion-exchange area coating (41).
13. preparation methods according to claim 12, is characterized in that, the integrated organic porous films of described perforated membrane.
14. preparation methods according to claim 12, it is characterized in that, described S1 specifically comprises: be dissolved in by ion exchange resin in the good solvent of described ion exchange resin and form the first polymer solution, described first polymer solution is coated to the zone line of described perforated membrane, remove the good solvent of described ion exchange resin, make described ion exchange resin film-forming.
15. preparation methods according to claim 14, it is characterized in that, further containing the inorganic nano ion of 0.01 ~ 25wt% in described first polymer solution, described inorganic nano-particle comprises nano silicon, nano titanium oxide, carbon nano-tube and derivative thereof or Graphene and derivative thereof.
16. preparation methods according to claims 14 or 15, is characterized in that, the surfactant further containing 0.01 ~ 5wt% in described first polymer solution.
17. preparation methods according to claim 12, is characterized in that, described S2 specifically comprises:
Encapsulant resin is dissolved in the good solvent of described encapsulant resin and forms the second polymer solution, described second polymer solution is coated to the region of described perforated membrane except described ion-exchange area coating (41), remove the good solvent of described encapsulant resin, make described encapsulant resin film-forming; Or
Carry out after anti-corrosive rubber is mixed with auxiliary agent mixingly obtaining mixing anti-corrosive rubber, described mixing anti-corrosive rubber is dissolved in the good solvent of described mixing anti-corrosive rubber and makes rubber cement, described rubber cement is coated to the region of described perforated membrane except described ion-exchange area coating (41), remove the good solvent of described mixing anti-corrosive rubber, make described mixing anti-corrosive rubber film-forming.
18. preparation methods according to claim 17, is characterized in that, described auxiliary agent is crosslinking agent.
19. preparation methods according to claim 12, is characterized in that, repeat described S1 and/or described S2 more than twice or twice.
20. preparation methods according to claim 12, is characterized in that, the pre-treatment step comprised described perforated membrane that takes a step forward of described S1: adopt ethanol or isopropyl alcohol to soak described perforated membrane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510543135.7A CN105140543A (en) | 2015-08-28 | 2015-08-28 | Flow cell ion exchange membrane assembly, preparing method of flow cell ion exchange membrane assembly and flow cell comprising flow cell ion exchange membrane assembly |
Applications Claiming Priority (1)
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| CN106229536A (en) * | 2016-08-31 | 2016-12-14 | 中国东方电气集团有限公司 | Electrolyte balance device and there is its flow battery |
| CN106558662A (en) * | 2015-09-28 | 2017-04-05 | 大连融科储能技术发展有限公司 | Ion-conductive membranes, using the flow battery and preparation method of the ion-conductive membranes |
| CN110867593A (en) * | 2019-11-29 | 2020-03-06 | 青海百能汇通新能源科技有限公司 | Composite diaphragm for flow battery and preparation method |
| CN116314986A (en) * | 2023-01-16 | 2023-06-23 | 山东东岳未来氢能材料股份有限公司 | Additive of flow battery film and high-performance flow battery film |
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