CN103515629A - Composite ultrafiltration or nanofiltration membrane for hydrogen-chlorine fuel cells, and preparation and application thereof - Google Patents
Composite ultrafiltration or nanofiltration membrane for hydrogen-chlorine fuel cells, and preparation and application thereof Download PDFInfo
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- CN103515629A CN103515629A CN201210222701.0A CN201210222701A CN103515629A CN 103515629 A CN103515629 A CN 103515629A CN 201210222701 A CN201210222701 A CN 201210222701A CN 103515629 A CN103515629 A CN 103515629A
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- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 239000000460 chlorine Substances 0.000 title claims abstract description 30
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 30
- 239000000446 fuel Substances 0.000 title claims abstract description 26
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title abstract description 12
- 238000001728 nano-filtration Methods 0.000 title abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 12
- 229920006393 polyether sulfone Polymers 0.000 claims description 11
- 239000004695 Polyether sulfone Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006277 sulfonation reaction Methods 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- GIIJTDXSACMUEI-UHFFFAOYSA-N carbonic acid;propane-1,1-diol Chemical compound OC(O)=O.CCC(O)O GIIJTDXSACMUEI-UHFFFAOYSA-N 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000006259 organic additive Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- CBWUNQZJGJFJLZ-UHFFFAOYSA-N [Cl].Cl Chemical compound [Cl].Cl CBWUNQZJGJFJLZ-UHFFFAOYSA-N 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 238000000614 phase inversion technique Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003321 amplification Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 239000002352 surface water Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241001529297 Coregonus peled Species 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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Classifications
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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
-
- 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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a composite ultrafiltration or nanofiltration membrane for hydrogen-chlorine fuel cells by using chlorine dissolved in hydrochloric acid as a raw material, which comprises the following steps: dissolving a high-molecular polymer substrate and a negatively charged polymer filler in an organic solvent under the action of ultrasonic to obtain a membrane preparation solution, and preparing the polymer composite ultrafiltration or nanofiltration membrane in an asymmetric configuration structure by a phase inversion method, wherein the thickness of the membrane is 25-250 mu m, and the porosity is 60-85%. The composite membrane can be well used in hydrogen-chlorine fuel cells.
Description
Technical field
The present invention relates to a kind of take be dissolved in Compound Ultrafiltration or NF membrane and preparation method thereof for hydrogen-chlorine fuel cell that the chlorine in hydrochloric acid is raw material, be specifically related to a kind of phase inversion that adopts and directly prepare the method for Hydrophilized porous membrane for hydrogen-chlorine fuel cell.
Background technology
Hydrogen-chlorine fuel cell using hydrogen as fuel, chlorine as oxidant, there is respectively electrochemical reaction in both, the chemical energy being stored in wherein is directly changed into electric energy in battery, can produce the hydrochloric acid of desired concn simultaneously.Therefore need a kind of electrolyte membrance that cathode and anode is isolated.Proton exchange membrane (PEM) is one of core component of Proton Exchange Membrane Fuel Cells (PEMFC), desirable PEM should have that proton conductivity is high, gas and low, the high ion selectivity of Test Liquid Permeability of Core, sufficiently high mechanical strength, thermal stability and chemical stability, and there is suitable cost performance.
At present, the research of hydrogen-chlorine fuel cell is also in the exploratory stage, according to literature search, (USP 4128701 only several pieces of documents and 4 patents both at home and abroad, CN 86104831, CN 1805196, JP3150803-U), but these patents are all the selection optimization about electrode materials such as battery system or catalyst, wherein electrolyte membrance all adopts business Nafion film or directly uses the solution such as hydrochloric acid as electrolyte, do not have the research about newtype dielectric film, and the cell cathode side raw material of finding report mostly is liquid (chlorine is dissolved in hydrochloric acid), anode-side is hydrogen, this feeding manner is similar to direct methanol fuel cell (DMFC), therefore can use for reference DMFC proton-conductive films.The people such as Peled have prepared a kind of nanoporous proton-conductive films, and it take the PVDF of doping silicon dioxide particle is raw material, and casting film in baking oven, adsorbs different acid solutions afterwards, has very high proton-conducting, and is successfully applied in DMFC.But this membrane porosity and adsorber acid amount are lower.We have set forth a kind of preparation method of polymer/inorganic oxide composite hyperfiltration membrane and the application in hydrogen-chlorine fuel cell thereof in patent 201210052189.x, illustrate that this perforated membrane can well be applied in hydrogen-chlorine fuel cell.And except inorganic oxide can be used as filler, some polymer with electric charge also can be used as perforated membrane filler, these charged polymer films can have certain charged repelling effect, have good separating property and higher ion selectivity.
Summary of the invention
Object of the present invention, except providing a kind of hydrogen-chlorine fuel cell with perforated membrane, is also to provide a kind of phase inversion that adopts directly to prepare the preparation method of Compound Ultrafiltration or NF membrane for hydrogen-chlorine fuel cell.
For achieving the above object, the technical solution used in the present invention can realize as follows:
By Compound Ultrafiltration or a NF membrane, it is by high molecular polymer substrate and the composite porous film prepared with the polymer filler of negative electrical charge; The polymer filler of negative electrical charge mass fraction in polymeric base layer is 0.5-20wt.%.
With high molecular polymer, can be hydrochloric acid or chlorine to be there is to poly-inclined to one side tetrafluoroethene (PVDF), Kynoar-hexafluoropropylene copolymer (PVDF-HFP), Phthalazinone polyether-ketone (PPEK), polysulfones (PSF) or the polyether sulfone (PES) of well tolerable property; Molecular weight is 10000-100000g mol
-1;
Electronegative polymer is mainly sulfonated polyether or SPSF, is sulfonated polyether ketone, sulfonated polyether-ether-ketone, SPSF or sulfonated polyether sulfone, and sulfonation degree is 20%-90%, and molecular weight is 10000-100000g mol
-1.
High boiling solvent used is the good solvent of high molecular polymer, is DMSO, DMF, DMAC or NMP;
Additive is glycerine, dimethyl carbonate, diethyl carbonate, carbonate propanediol fat, PVP or LiCl.
Described Compound Ultrafiltration or NF membrane are the perforated membranes of asymmetric configuration structure, it consists of dense layer surface and loose porous basic unit, the perforated membrane that refers to the asymmetric configuration structure consisting of same material is the porosity of a side and porosity and the aperture that aperture is all less than opposite side, forms the perforated membrane of the asymmetric configuration structure consisting of dense layer surface and loose porous basic unit; Maybe can be described as: described Compound Ultrafiltration or NF membrane are the perforated membranes of asymmetric configuration structure, refer to have and arrange the fine and close top layer of orderly micropore and take the perforated membrane of finger-like pore structure as the asymmetric configuration structure of main bottom.
The preparation method of described composite membrane: in high boiling organic solvent and additive mixed solution, adopt phase inversion preparation to there is the composite porous film of asymmetric configuration structure high molecular polymer substrate and electronegative polymer filler ultrasonic dissolution.
Be specially;
A. prepare casting solution, comprise and account for the polymeric substrates that casting solution mass fraction is 5-25wt.%, with the negatively charged polymer filler that accounts for polymer 0-20wt.%, wherein electronegative polymer is mainly sulfonated polymer material, as sulfonated polyether class or SPSF class.Solvents is the high boiling solvents such as DMSO, DMF, DMAC and NMP of 60-95wt.% and the mixed solution of 0-35wt.% additive, and wherein additive can be glycerine, dimethyl carbonate, diethyl carbonate, carbonate propanediol fat, PVP or LiCl etc.;
B. above-mentioned casting solution stirs 0.5-20h under temperature 20-100 ° C, ultrasonic 0.5-3h, and the uniform polymeric solution obtaining static or vacuum defoamation 0.5-10h under temperature 20-90 ° C makes final casting solution;
C. adopt scraper by above-mentioned casting solution blade coating on glass plate, by regulating scraper height to carry out the thickness of controlling diaphragm, the film thickness making is 25-250 μ m;
D. glass plate is flatly put in the coagulating bath that temperature is 20-80 ° of C, after static 0.5-24h, taken out, dry in air after film is soaked to 0.5-24h in absolute ethyl alcohol or n-hexane;
E. the film drying is processed after 0.5-10h under temperature 20-90 ° C in concentration 1-6M hydrochloric acid solution, can in hydrogen-chlorine fuel cell, be used.
The present invention can be that hydrochloric acid or chlorine are had to poly-inclined to one side tetrafluoroethene (PVDF), the Kynoar-hexafluoropropylene copolymer (PVDF-HFP) of well tolerable property, polyether-ether-ketone, Phthalazinone polyether-ketone (PPEK), polysulfones (PSF) or the polyether sulfone (PES) etc. of sulfonation for the preparation of hydrogen-chlorine fuel cell with the polymer that Compound Ultrafiltration or NF membrane adopt, consider liquid hydrochloric acid and chlorine gas environment in hydrogen-chlorine fuel cell running, optimum should be to have fine chemical stability and hydrophilic polyether sulfone.Perforated membrane average pore size prepared by the present invention is about 0.5-25nm, and porosity is 60-85%, and water absorption rate is 150-350%, and minimum bubbling pressure is 0.2-1.5MPa.
Tool of the present invention has the following advantages:
1. method of operation is simple, easily go, the Compound Ultrafiltration of making or NF membrane thickness, membrane porosity, membrane aperture size and filler doping are easy to control, protect acid amount high, intensity is good, and cost is low, environmental friendliness, safe and reliable, is easy to large-scale production, can be advantageously applied in hydrogen-chlorine fuel cell.
2. hydrogen-chlorine fuel cell all adopts business Nafion film or PBI-H at present
3pO
4high temperature membrane, the present invention is applied to, in hydrogen-chlorine fuel cell, to have novelty by perforated membrane.
3. adopt the present invention to prepare composite membrane hydrogen-chlorine fuel cell performance and be better than Du Pont's public affairs that thickness is close
Take charge of the battery performance of business-like Nafion 212 film assemblings.
Accompanying drawing explanation
Fig. 1 is film surface and the photo of film section under scanning electron microscopy of the pure poly (ether-sulfone) ultrafiltration membrane of embodiment 1 preparation: a) surface; B) section; C) section amplification figure;
Fig. 2 be embodiment 2 preparation containing 2wt.%SPEEK(sulfonation degree 57%) polyether sulfone composite nanometer filtering film film surface and the photo of film section under scanning electron microscopy: a) surface; B) section; C) section amplification figure;
Fig. 3 is the battery performance curve chart of embodiment 2;
Fig. 4 be embodiment 3 preparation containing 6wt.%SPEEK(sulfonation degree 57%) polyether sulfone composite nanometer filtering film film surface and the photo of film section under scanning electron microscopy: a) surface; B) section; C) section amplification figure;
Fig. 5 is the battery performance curve chart of embodiment 3;
Fig. 6 be embodiment 4 preparation containing 2wt.%SPEEK(sulfonation degree 78%) polyether sulfone composite nanometer filtering film film surface and the photo of film section under scanning electron microscopy: a) surface; B) section; C) section amplification figure;
Fig. 7 is the performance comparison diagram of the Nafion212 film assembled battery of embodiment 4 and E.I.Du Pont Company.
Embodiment.
Embodiment 1: by the highly purified polyether sulfone of 1g (PES, molecular weight M
w=58000), the analytically pure NMP of 4.6g and 0.3g LiCl mix, 60 ° of C lower magnetic forces stir 5h, ultrasonic mixing 1h, static 3h deaeration under room temperature, striking film forming under room temperature, occurs in the water under room temperature by liquid phase to the inversion of phases of solid phase and film forming (thickness is 100 μ m), film is soaked in absolute ethyl alcohol to 4h after during 2h, in 1M hydrochloric acid, 40 ° of C boil 3h, put in watery hydrochloric acid stand-by.Gained film has dissymmetrical structure (film surface and section electromicroscopic photograph are shown in accompanying drawing 1), the contact angle of the film surface water droplet of Surface Contact angle tester test is 78.7 °, mercury injection method test porosity is 81.69%, poor heavy method test water absorption rate is 297.56%, mercury injection method test average pore size is 11.64nm, smallest bubbles point pressure is 0.24MPa, and by the film surface liquid wiped clean of boiling in acid, adopting two sonde methods to test ionic conductance under its room temperature is 31.34mS cm
-1.
Embodiment 2: by 0.9g PES(M
w=58000), 0.018g SPEEK(sulfonation degree is 57%), 4.2g DMF and 0.26g PVP mix, under room temperature, stir 1h, ultrasonic mixing 0.5h, 60 ° of C vacuum defoamation 1h, under room temperature on glass plate knifing, inversion of phases film forming in 30 ° of C water (film thickness 80 μ m), soaks in n-hexane 1 day, in air, dry, in 3M hydrochloric acid, 80 ° of C boil 1h.Gained film has dissymmetrical structure (film surface and section electromicroscopic photograph are shown in accompanying drawing 2), the contact angle of gained film surface water droplet is 64.6 °, porosity is 81.10%, water absorption rate is 284.1%, average pore size is 2.69nm, smallest bubbles point pressure is 0.43MPa, and by the film surface liquid wiped clean of boiling in acid, testing ionic conductance under its room temperature is 36.11mS cm
-1.
Adopt method described in patent CN02127802.4 to prepare hydrophilic negative electrode (catalyst is 70%Pt/C), in electrode, catalyst Pt carrying capacity is 1mg cm
-2.Anode adopts commercialization gas-diffusion electrode (newly driving source company), and in electrode, catalyst Pt carrying capacity is 0.4mg cm
-2.For guaranteeing that electrode and the effective of film contact, reduce the contact resistance between electrode and film, negative electrode and anode are placed in respectively to prepared film both sides (film compacted zone is towards anode), in hydraulic press, under 100 ° of C and 0.1MP, suppress 1min, taking-up is cooling rapidly, obtains membrane electrode three-in-one (MEA).
Gained MEA is assembled into fuel cell, test battery performance on monocell evaluating apparatus.Test performance curve is shown in accompanying drawing 3.Battery-operated condition is as follows: battery temperature is 40 ° of C, hydrogen flow rate 110mlmin
-1, without humidification, normal pressure, chlorine is first dissolved in 3M HCl, enters cell cathode afterwards by peristaltic pump, and flow velocity is 850ml min
-1.
Embodiment 3: by 1gPES(M
w=58000), 0.064g SPEEK(sulfonation degree is 57%), 4g DMAC and the ultrasonic mixing of 0.25g glycerine 3h, under room temperature, stir 5h, deaeration in 60 ° of C vacuum drying ovens, knifing in room temperature lower glass plate, put into afterwards inversion of phases film forming in 50 ° of C water (80 μ m), after 4h, film is soaked in absolute ethyl alcohol to 12h, in 3M hydrochloric acid, 60 ° of C boil 3h, put in watery hydrochloric acid stand-by.Gained film has dissymmetrical structure (film surface and section electromicroscopic photograph are shown in accompanying drawing 4), the contact angle of gained film surface water droplet is 66.6 °, porosity is 73.51%, water absorption rate is 184.96%, average pore size is 1.01nm, smallest bubbles point pressure is 0.31MPa, and by the film surface liquid wiped clean of boiling in acid, testing ionic conductance under its room temperature is 30.34mS cm
-1.
Adopt this film preparation MEA, the electrode of employing and preparation method, with embodiment 2, prepare MEA by the Nafion115 of business according to the method for implementing in 2, the more than test battery performance of two MEA on monocell evaluating apparatus.The operating condition of battery is with embodiment 2.Test battery performance curve is shown in accompanying drawing 5.
Embodiment 4: by 0.9g PES(M
w=58000), 0.018g SPEEK(sulfonation degree 78%), 4g DMSO and the ultrasonic mixing of 0.25gPVP 3h, under room temperature, stir 5h, deaeration in 60 ° of C vacuum drying ovens, knifing in room temperature lower glass plate, put into afterwards inversion of phases film forming in 50 ° of C water (120 μ m), after 4h, film is soaked in absolute ethyl alcohol to 12h, in 3M hydrochloric acid, 60 ° of C boil 3h, put in watery hydrochloric acid stand-by.Gained film has dissymmetrical structure (film surface and section electromicroscopic photograph are shown in accompanying drawing 6), the contact angle of gained film surface water droplet is 70.0 °, porosity is 82.35%, water absorption rate is 317.65%, average pore size is 20.39nm, smallest bubbles point pressure is 0.85MPa, and by the film surface liquid wiped clean of boiling in acid, testing ionic conductance under its room temperature is 37.35m S cm
-1.
Adopt this film preparation MEA, the electrode of employing and preparation method, with embodiment 2, prepare MEA by the Nafion212 of business according to the method for implementing in 2, the more than test battery performance of two MEA on monocell evaluating apparatus.The operating condition of battery is with embodiment 2.Test battery performance curve is shown in accompanying drawing 7.
Claims (8)
1. Compound Ultrafiltration or a NF membrane for hydrogen-chlorine fuel cell, is characterized in that:
It is Compound Ultrafiltration or the NF membrane of being prepared by high molecular polymer substrate and electronegative polymer filler, and uniform filling is distributed in substrate; In ultrafiltration or NF membrane, electronegative polymer filler mass fraction is 0.5-20wt.%.
2. according to Compound Ultrafiltration claimed in claim 1 or NF membrane, it is characterized in that:
High molecular polymer used is hydrochloric acid or chlorine to be had to poly-inclined to one side tetrafluoroethene (PVDF), Kynoar-hexafluoropropylene copolymer (PVDF-HFP), Phthalazinone polyether-ketone (PPEK), polysulfones (PSF) or the polyether sulfone (PES) of well tolerable property;
Electronegative polymer is mainly sulfonated polyether or the SPSF in sulfonated polymer material.
3. according to Compound Ultrafiltration claimed in claim 2 or NF membrane, it is characterized in that:
Poly-inclined to one side tetrafluoroethene (PVDF), Kynoar-hexafluoropropylene copolymer (PVDF-HFP), Phthalazinone polyether-ketone (PPEK), polysulfones (PSF) or polyether sulfone (PES) molecular weight are 10000-100000g mol
-1;
Sulfonated polyether or SPSF are sulfonated polyether ketone, sulfonated polyether-ether-ketone, SPSF or sulfonated polyether sulfone, and sulfonation degree is 20%-90%, and molecular weight is 10000-100000g mol
-1.
4. according to the Compound Ultrafiltration described in claim 1 or 2 or NF membrane, it is characterized in that:
Described Compound Ultrafiltration or NF membrane are the perforated membranes of asymmetric configuration structure, it consists of dense layer surface and loose porous basic unit, the perforated membrane that refers to the asymmetric configuration structure consisting of same material is the porosity of a side and porosity and the aperture that aperture is all less than opposite side, forms the perforated membrane of the asymmetric configuration structure consisting of dense layer surface and loose porous basic unit.
5. the preparation method of Compound Ultrafiltration or NF membrane described in a claim 1,2,3 or 4, it is characterized in that: in high boiling organic solvent and additive mixed solution, adopt phase inversion preparation to there is Compound Ultrafiltration or the NF membrane of asymmetric configuration structure high molecular polymer and electronegative polymer filler ultrasonic dissolution.
6. according to preparation method claimed in claim 5, it is characterized in that:
A. prepare casting solution, comprise and account for the polymeric substrates that casting solution mass fraction is 5-25wt.%, solvents is the mixed solution of 60-95wt.% high boiling solvent and 0-35wt.% additive; And their three's mass fraction sums are 100%;
The electronegative polymer filler of the 0.5-20wt.% that accounts for polymeric substrates and electronegative polymer filler quality sum also adding in casting solution;
B. above-mentioned casting solution stirs 0.5-20h under temperature 20-100 ° C, ultrasonic 0.5-3h, and the uniform polymeric solution obtaining static or vacuum defoamation 0.5-10h under temperature 20-90 ° C makes final casting solution;
C. adopt scraper by above-mentioned casting solution blade coating on glass plate, by regulating scraper height to carry out the thickness of controlling diaphragm, the film thickness making is 25-250 μ m;
D. glass plate is flatly put in the coagulating bath that temperature is 20-80 ° of C, after static 0.5-24h, taken out, dry in air after film is soaked to 0.5-24h in absolute ethyl alcohol or n-hexane;
E. the film drying is processed after 0.5-10h under temperature 20-90 ° C in concentration 1-6M hydrochloric acid solution, can in hydrogen-chlorine fuel cell, be used.
7. according to preparation method claimed in claim 6, it is characterized in that:
High boiling solvent used is good solvent DMSO, DMF, DMAC or the NMP of high molecular polymer;
Additive is glycerine, dimethyl carbonate, diethyl carbonate, carbonate propanediol fat, PVP or LiCl;
Coagulating bath is the running water of 20-80 ° of C.
8. an application for Compound Ultrafiltration or NF membrane described in claim 1,2,3 or 4, is characterized in that: described ultrafiltration or NF membrane can be used as in the hydrogen-chlorine fuel cell that electrolyte membrance is dissolved in hydrochloric acid chlorine for take is raw material.
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| CN201210222701.0A CN103515629B (en) | 2012-06-29 | 2012-06-29 | A kind of hydrogen-chlorine fuel cell Compound Ultrafiltration or NF membrane and Synthesis and applications thereof |
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