CN105789668B - The preparation method of metal-organic framework materials/polymer composite proton exchange membrane - Google Patents
The preparation method of metal-organic framework materials/polymer composite proton exchange membrane Download PDFInfo
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- CN105789668B CN105789668B CN201610119969.XA CN201610119969A CN105789668B CN 105789668 B CN105789668 B CN 105789668B CN 201610119969 A CN201610119969 A CN 201610119969A CN 105789668 B CN105789668 B CN 105789668B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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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 a kind of preparation methods of metal-organic framework materials/polymer composite proton exchange membrane, it is characterized in that by polymeric matrix and a certain amount of metal-organic framework materials are with organic solvent dissolving and ultrasonic disperse is at uniform film liquid, obtained film liquid is coated in the glass pane surface of flat smooth, then organic solvent is removed to obtain composite membrane, then vanadium redox battery compound proton exchange membrane is prepared in composite membrane vacuum drying afterwards for 24 hours.The compound proton exchange membrane surfacing, film internal structure is regular, the uniform zero defect of film thickness, and thickness is 10~300 μm.The compound proton exchange membrane of the present invention has the ability of splendid barrier vanadium ion infiltration, while keeping excellent proton transport performance, overcomes existing vanadium redox battery diaphragm vanadium ion and permeates larger disadvantage；Simple with preparation process, proton transmitance is high, and resistance vanadium performance is splendid, and oxidative resistance is excellent, is easy to the advantages that industry is amplified.
Description
Technical field
The present invention relates to proton exchange field of membrane preparation, more particularly to a kind of for vanadium redox battery
The preparation method of metal-organic framework materials/polymer composite proton exchange membrane.
Background technology
Present Global energy and environment problem is on the rise, it has also become restricts the bottle of countries in the world economy and social development
Neck greatly develops the regenerative resource of clean and effective, such as wind energy, solar energy, water energy and geothermal energy, it has also become solves the energy and asks
The outlet of topic.But due to the limitation of natural conditions, its generated energy generates significant changes with day-night change for wind energy and solar energy, difficult
In keeping stable electric energy output, needs to coordinate with the apparatus for storing electrical energy of certain scale, just can guarantee continual and steady electric energy
Supply.Therefore the energy-storage system that exploitation electric energy conversion efficiency is high, storage volume is big, economic performance is good becomes Renewable Energy Development
Key.
Vanadium redox battery（Vanadium Redox Flow Battery, abbreviation VRB）It is a kind of efficient
, large capacity, green new cleaning fuel energy storage device.VRB is mainly made of electrode material, battery diaphragm and electrolyte,
Septation restricts always the hair of vanadium cell as one of the key position in VRB, the efficiency of structure and performance decision battery
Exhibition.It, which acts on not only plaing a part of to separate positive and negative anodes, prevents battery short circuit, but also allows charge carrier in battery charging and discharging
（H+, HSO4 -Deng）It passes freely through and ensures positive and negative two-stage charge balance and constitute cell circuit.Ideal vanadium redox
Battery diaphragm should have following features：（1）Hydrogen ion（Proton）Transmitance is high, and film resistance is small, and voltage efficiency is high；（2）Vanadium ion
Transmitance is low, and cross contamination is small, reduces self-discharge of battery, improves energy efficiency；（3）With certain mechanical strength, chemically-resistant
Burn into resistance to oxidation, has extended cycle life, and price is low；（4）When battery charging and discharging water transit dose is small, keeps anode, catholyte
Water balance.From the point of view of the battery diaphragm being just commercialized at present, there are no a kind of proton exchange membrane can fully meet above-mentioned requirements.At present
Most commonly used is the Nafion membrane of E.I.Du Pont Company's production, although high with ionic conductivity, good chemical stability,
It is that it is poor to the block of vanadium ion, has apparent water transport phenomena in charge and discharge process, cause self-discharge phenomenon more serious,
It is at high price simultaneously, the needs of extensive energy storage cannot be met, these factors limit vanadium redox battery industry
The development of change.Researcher has carried out a large amount of improvement.Patent（CN103022400A）It is raw material using polymer, by dense
Sulfonated polymer is made in sulfuric acid sulfonation；Then the polysulfones additive of different proportion is added, stirring is formed a film after a certain period of time
Solution；The film build methods such as the tape casting, coating method, cement-dipping method are recycled to prepare sulfonated polymer diaphragm；Or by polymer film
It is clipped among two layers of polytetrafluoroethylene (PTFE) screen cloth and battery diaphragm is made.These polymer film stability are preferable, easy to operate, technique is simple
It is single, but film is susceptible to fault of construction in preparation process, influences final performance.
Metal-organic framework materials（Metal-organic Frameworks, abbreviation MOF）By the extensive of researcher
Concern, with porous structure and very abundant internal gutter, this makes the application of MOF materials also quite wide, but by its
Report for proton exchange membrane is also seldom.
Invention content
The metal-organic framework materials that the purpose of the present invention is to provide a kind of for vanadium redox battery/poly-
Close the preparation method of object compound proton exchange membrane.
The preparation method of metal-organic framework materials/polymer composite proton exchange membrane of the present invention contains following successively
Step：
1) polymeric matrix and a certain amount of metal-organic framework materials organic solvent are dissolved into simultaneously ultrasonic disperse Cheng Jun
Even film liquid, polymeric matrix concentration in film liquid are expressed as 3~50% with mass percent；The metal organic framework
The quality of material accounts for the 0.01~50% of polymer matrix weight；
2) by step 1）Obtained film liquid is coated in the glass pane surface of flat smooth, then again removes organic solvent
To composite membrane；
3) by step 2）The vanadium redox battery is prepared for 24 hours in obtained composite membrane vacuum drying
Use compound proton exchange membrane.
The polymeric matrix be polyethylene, polypropylene, polyether-ketone, polyether-ether-ketone, polyarylene ether ketone, polyethersulfone ketone,
Polyetherimide, polysulfones, polyether sulfone, polybenzimidazoles, polyacrylonitrile, polytetrafluoroethylene (PTFE), Kynoar, is gathered polyimides
The mixture of one or more of vinyl alcohol, polyethylene-TFE copolymer, polyphenylene oxide or polyethylene glycol oxide；
The polymeric matrix can also be polyethylene, polypropylene, polyether-ketone, polyether-ether-ketone, polyarylene ether ketone, polyethers
Sulfone ketone, polyetherimide, polyimides, polysulfones, polyether sulfone, polybenzimidazoles, polyacrylonitrile, polytetrafluoroethylene (PTFE), polyvinylidene fluoride
Alkene, polyvinyl alcohol, polyethylene-TFE copolymer, polyphenylene oxide or polyethylene glycol oxide carry out sulfonation modifying or quaternised modified
What is obtained is polymer-modified；
The polymeric matrix can also be containing polyethylene, polypropylene, polyether-ketone, polyether-ether-ketone, polyarylene ether ketone,
Polyethersulfone ketone, polyimides, polysulfones, polyether sulfone, polybenzimidazoles, polyacrylonitrile, polytetrafluoroethylene (PTFE), gathers partially at polyetherimide
Vinyl fluoride, polyvinyl alcohol, polyethylene-TFE copolymer, polyphenylene oxide, polyethylene glycol oxide or by these above-mentioned polymeric matrixs
By sulfonation modifying or quaternised modified obtained one or more of polymer-modified mixture；
The metal-organic framework materials are ZIF series（Zeolitic imidazolate frameworks）, MIL systems
Row（materiauxs de I’Institut Lavoisier）, COF series（covalent organic framework）、
RPF series（rare-earth polymeric framework）, MPF series（metal peptide framework）、
The mixture of one or more of UiO-66 or MOF-5；
The organic solvent is toluene, tetrahydrofuran, dioxane, dimethylbenzene, dichloromethane, dichloroethanes, tri-chlorination
Carbon, carbon tetrachloride, hexamethylene, dimethylformamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or dense sulphur
The mixture of one or more of acid；
The method of the removal organic solvent can be that molten causes phase separation removes solvent method, can also be directly heat make it is molten
Agent volatility process；
The thickness of the vanadium redox battery compound proton exchange membrane is 10~300 μm；
The vanadium redox battery compound proton exchange membrane can be apertured polymeric film, and aperture size is
0.5~200nm can also be the non-porous film of densification.
Compared with prior art, the present invention having following advantage：
1）The preparation method of compound proton exchange membrane of the present invention is to introduce to contain mesoporous knot in a polymer matrix
The metal-organic framework materials of structure, using volume excluding effect make the compound proton exchange membrane of preparation have splendid barrier vanadium from
The ability of son infiltration；
2）Different types of metal-organic framework materials have different apertures, have by changing polymeric matrix and metal
The compound proton exchange membrane that the type of machine framework material can be had excellent performance；
3）Film-forming method of the present invention is simple, and amplification production easy to implement, the composite film surface is smooth, inside film
Compound with regular structure, the uniform zero defect of film thickness；
4）The compound proton exchange membrane of the present invention is suitable for vanadium redox battery, can be used for proton exchange
Membrane cell；
5）Whole vanadium oxide reduction liquid of the advantage that metal-organic framework materials duct in the present invention is adjustable to Development of Novel
Galvanic battery diaphragm provides new approaches.
Specific implementation mode
Embodiment 1
By 0.01g MOF-5,1g sulfonated polyimides and 1g polyvinyl alcohol are placed in conical flask, and it is sub- that 24g dimethyl is added
Sulfone, 80 DEG C of heating stirring 48h, then room temperature ultrasound 2h be prepared into finely dispersed film liquid.Film liquid is coated in flat smooth
Glass pane surface is dried solvent with infrared lamp, is then placed into 100 DEG C of dryings in vacuum and for 24 hours, is obtained the compound of 60 μm of thickness
Film.
Embodiment 2
0.1g ZIF-8 and 2g polytetrafluoroethylene (PTFE) is placed in conical flask, 19g dimethylformamides are added, 80 DEG C of heating are stirred
48h is mixed, then room temperature ultrasound 2h is prepared into finely dispersed film liquid.Film liquid is coated in the glass pane surface of flat smooth, soon
Speed into the water cements out solvent, is then placed into 100 DEG C of dryings in vacuum and for 24 hours, obtains the composite membrane of 100 μm of thickness.
Embodiment 3
1g MIL-101 and 2g sulfonated polyether sulfone ketone is placed in conical flask, addition 10g N-Methyl pyrrolidones, 80 DEG C
Heating stirring 48h, then room temperature ultrasound 2h be prepared into finely dispersed film liquid.Film liquid is coated in the glass plate table of flat smooth
Solvent is dried with infrared lamp in face, is then placed into 100 DEG C of dryings in vacuum and for 24 hours, obtains the composite membrane of 20 μm of thickness.
Embodiment 4
The quaternized polyetherimide of 0.5g UiO-66 and 2g is placed in conical flask, 14g dichloromethane is added, 80 DEG C add
Thermal agitation 48h, then room temperature ultrasound 2h be prepared into finely dispersed film liquid.Film liquid is coated in the glass plate table of flat smooth
Face quickly into the water cements out solvent, is then placed into 100 DEG C of dryings in vacuum and for 24 hours, obtains answering for 200 μm of thickness
Close film.
The performance of compound proton exchange membrane prepared by 1 present invention of table in vanadium redox battery
| Composite membrane forms | Proton conductivity （mS/cm2） | Vanadium ion permeability（10-7 × cm2/min） | Coulomb Efficiency | Voltage is imitated Rate | Energy Efficiency | |
| Embodiment 1 | MOF-5/ sulfonation polyamides is sub- Amine/polyvinyl alcohol | 55 | 1.314 | 97.5 | 92.21 | 89.88 |
| Embodiment 2 | ZIF-8/ polytetrafluoroethylene (PTFE) | 70 | 1.178 | 98.9 | 92.15 | 91.13 |
| Embodiment 3 | MIL-101/ sulfonated polyethers Sulfone ketone | 66 | 1.234 | 98.0 | 91.89 | 90.05 |
| Embodiment 4 | UiO-66/ is quaternized poly- Etherimide | 64 | 0.853 | 99.8 | 91.80 | 91.79 |
Claims (6)
1. the vanadium redox battery preparation method of metal-organic framework materials/polymer composite proton exchange membrane,
It is characterized in that, containing following steps successively：
1) by polymeric matrix and a certain amount of metal-organic framework materials are with organic solvent dissolving and ultrasonic disperse is at uniform
Film liquid, polymeric matrix concentration in film liquid are expressed as 3~50% with mass percent；The metal-organic framework materials
Quality account for the 0.01~50% of polymer matrix weight；The metal-organic framework materials are ZIF series, COF series, RPF
The mixture of one or more of series, MPF series, UiO-66 or MOF-5；
2) film liquid for obtaining step 1) is coated in the glass pane surface of flat smooth, then again removes organic solvent and is answered
Close film；
3) the vanadium redox battery gold is prepared for 24 hours in the composite membrane vacuum drying that step 2) obtains
Belong to organic framework material/polymer composite proton exchange membrane.
2. the vanadium redox battery according to claim 1 compound matter of metal-organic framework materials/polymer
The preparation method of proton exchange, which is characterized in that the polymeric matrix be polyethylene, polypropylene, polyether-ketone, polyether-ether-ketone,
Polyarylene ether ketone, polyetherimide, polyimides, polysulfones, polyether sulfone, polybenzimidazoles, polyacrylonitrile, gathers polyethersulfone ketone
One kind in tetrafluoroethene, Kynoar, polyvinyl alcohol, polyethylene-TFE copolymer, polyphenylene oxide or polyethylene glycol oxide
Or several mixture.
3. the vanadium redox battery according to claim 1 compound matter of metal-organic framework materials/polymer
The preparation method of proton exchange, which is characterized in that the polymeric matrix be polyethylene, polypropylene, polyether-ketone, polyether-ether-ketone,
Polyarylene ether ketone, polyetherimide, polyimides, polysulfones, polyether sulfone, polybenzimidazoles, polyacrylonitrile, gathers polyethersulfone ketone
Tetrafluoroethene, Kynoar, polyvinyl alcohol, polyethylene-TFE copolymer, polyphenylene oxide or polyethylene glycol oxide carry out sulfonation
It is modified or it is quaternised modified obtain it is polymer-modified.
4. the vanadium redox battery according to claim 1 compound matter of metal-organic framework materials/polymer
The preparation method of proton exchange, which is characterized in that the polymeric matrix is containing polyethylene, polypropylene, polyether-ketone, polyethers ether
Ketone, polyarylene ether ketone, polyethersulfone ketone, polyetherimide, polyimides, polysulfones, polyether sulfone, polybenzimidazoles, polyacrylonitrile,
Polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol, polyethylene-TFE copolymer, polyphenylene oxide, polyethylene glycol oxide or will be upper
State these polymeric matrixs by sulfonation modifying or it is quaternised modified obtain it is polymer-modified in several mixtures.
5. the vanadium redox battery according to claim 1 compound matter of metal-organic framework materials/polymer
The preparation method of proton exchange, which is characterized in that the organic solvent is toluene, tetrahydrofuran, dioxane, dimethylbenzene, two
Chloromethanes, dichloroethanes, carbon trichloride, carbon tetrachloride, hexamethylene, dimethylformamide, dimethylacetylamide, dimethyl are sub-
The mixture of one or more of sulfone, N-Methyl pyrrolidone or the concentrated sulfuric acid.
6. the vanadium redox battery according to claim 1 compound matter of metal-organic framework materials/polymer
The preparation method of proton exchange, which is characterized in that the method for the removal organic solvent is molten cause phase separation removal solvent method, or
Person is to directly heat to make solvent evaporation method.
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