CN105958093B - A kind of fat guanidinium ion graphene oxide doped type composite anion film and preparation method thereof - Google Patents
A kind of fat guanidinium ion graphene oxide doped type composite anion film and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- ISNICOKBNZOJQG-UHFFFAOYSA-O guanidinium ion Chemical compound C[NH+]=C(N(C)C)N(C)C ISNICOKBNZOJQG-UHFFFAOYSA-O 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 150000001450 anions Chemical class 0.000 title claims abstract description 19
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 27
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 23
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 28
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 28
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- 150000002357 guanidines Chemical class 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 7
- -1 dichloromethane Alkane Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 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 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920002530 polyetherether ketone Polymers 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 4
- 239000003599 detergent Substances 0.000 claims 4
- 238000005119 centrifugation Methods 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 125000001246 bromo group Chemical class Br* 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 33
- 125000000129 anionic group Chemical group 0.000 abstract description 12
- 239000000446 fuel Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- 238000004108 freeze drying Methods 0.000 description 12
- 238000002604 ultrasonography Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 230000031709 bromination Effects 0.000 description 6
- 238000005893 bromination reaction Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- 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
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of fatty guanidinium ion graphene oxide doped type composite anion film and preparation method thereof, for the composite anion film composite membrane using polymer as matrix, fatty guanidine graphene oxide is ionization reagent, carries out ultrasonic disperse and is mixed with.There is the fatty guanidine radicals of the ionization reagent of such film resonance effects the distribution of positive charge to be made more to disperse, and the chemical stability under alkaline environment is preferable；Ion-conducting groups are located at surface of graphene oxide, can avoid being degraded by the main polymer chain that ion radical promotes；In addition, the introducing of graphene oxide also contributes to improve the mechanical strength of film.Anionic membrane prepared by the present invention has high stability, is suitble to apply in terms of alkaline fuel cell.
Description
Technical field
The invention belongs to fuel cell field of membrane material, and it is compound to be related to a kind of fatty guanidinium ion graphene oxide doped type
Anionic membrane and preparation method thereof.
Background technology
Hydrogen oxygen alkalinity membrane cell is a kind of novel zero-emission clean energy technology towards energy and environment problem.
Relative to proton membrane fuel battery, non-precious metal catalyst, low etc. excellent without carbonate crystallization, fuel permeability can be used by having
Point.But its development is restricted by critical material, and high performance anion alkaline membrane is an importance.
Core key position one of of the anionic membrane as alkaline fuel cell, directly affects the service life length of fuel cell
And operational effect.But two big main problem of poor chemical stability in its there are conductivity low, alkaline environment.Therefore, how to improve
The chemical stability and conductivity of anionic membrane become urgent problem.
Currently, hybrid inorganic-organic is to be modified a kind of advanced method to anionic membrane, i.e., introduced in organic material inorganic
Material.Inorganic material has high thermal stability, preferable chemical stability and mechanical stability, and introducing inorganic constituents can improve
The performance of film.[Ingratta.,et al.,Macromol.,2011,44,2074-2083.],[Ravi P.,et al.,
J.Membr.Sci.,2012,469,478-487.],[Zarrin,H.,et al.,ACS Nano,2015,9,2028-2037.]
Organic/inorganic composite film is prepared etc. zirconium dioxide, silica, graphene oxide is respectively adopted, the results showed that nano-particle draws
Enter to improve the stability of anionic membrane.
In Chinese patent CN 104835932A, zirconium dioxide is added imidazoles polyether-ether-ketone and prepared by Cheng Dandan et al.
Composite anion film, since there is zirconium dioxide certain hydrophily and mechanical stability, the conductivity and alkaline stability of film all to obtain
It improves to a certain extent.
In addition, innovation ionic group can be used and design the two large problems of the structural improvement film of film.The bases such as imidazoles and guanidine type
There is ion radical resonance effects to make the delocalized distribution of charge for group, to reduce positive charge density, reduction and phase interaction hydroxy
With inhibition or the degradation of retaining ion base to a certain extent.[Liu,L.,et al.,J.Membrane Sci.,2014,453,
52-60.] it is prepared for guanidine radicals anion-exchange membrane, the results showed that and the stability of film is increased.Simultaneously by designing film
Structure is also to improve a kind of method of film properties, and [Xu.T., et al., Scientific Reports, 2014,4,6486.] is set
Stick cable architecture has been counted, has as a result confirmed that ionic group is conducive to improve the stability of film far from main chain.
Invention content
The present invention proposes cloudy for two large problems-conductivity is low existing for above-mentioned anion-exchange membrane and alkaline stability is poor
The charge height of amberplex ion radical is delocalized and the new approaches that are detached with polymer chain, builds fatty guanidinium ionization oxidation
The composite anion film of graphene doping.
The composite anion film due to guanidinium ion conjugation and with the delocalized feature of charge height, can weaken with
The interaction of conducted ion is easy to ionize, is conducive to ionic conduction, and film is made to obtain height under relatively low degree of ionization
Conductivity, the swelling problem for avoiding high ionization from bringing；Ion radical is located at surface of graphene oxide, can avoid ion radical and accelerates to gather
Close owner's chain degradation；The introducing of graphene oxide also contributes to improve the mechanical strength of film.Such composite anion film tool simultaneously
There is higher stability.
In order to achieve the above object, the technical scheme is that：
A kind of fat guanidinium ion graphene oxide doped type composite anion film, using polymer as main chain, with fat
Guanidinium ion graphene oxide is ionization reagent, and composite anion film is prepared in main chain and ionization reagent ultrasonic mixing.
The polymer is polysulfones, polyphenylene oxide or polyether-ether-ketone.
A kind of preparation method of above-mentioned fatty guanidinium ion graphene oxide doped type composite anion film, including walk as follows
Suddenly：
The first step prepares guanidine salt Vilsmeyer salt
Under inert conditions, tetramethylurea is dissolved in solvent A and obtains mixed solvent, in the mixed solvent with 1~5 drop/s
Oxalyl chloride is added dropwise in speed, is warming up to 60 DEG C of condensing refluxes and reacts 1~10 hour, solvent A is removed after reaction, what is obtained is white or light
Yellow powdery solid is guanidine salt Vilsmeyer salt；The tetramethylurea, solvent A, oxalyl chloride volume ratio be 1：2
~10：1~1.2；The solvent is toluene, dichloromethane or ether.
Second step prepares silane guanidine reagent
Under inert conditions, the above-mentioned guanidine salt Vilsmeyer salt that prepare are dissolved in silane reagent, stirring at normal temperature makes guanidine
Salt Vilsmeyer salt are completely dissolved；Back flow reaction 24~48 hours after being warming up to 80 DEG C, obtain rufous thick liquid i.e.
For silane guanidine reagent.The silane reagent is 3- TSL 8330s or 3-aminopropyltriethoxysilane；
The molar ratio of the guanidine salt, silane reagent is 1：1.5~2.
Third walks, and prepares the guanidinated graphene oxide of fat
0.5g graphene oxides are taken to be dissolved in 300ml absolute ethyl alcohols, strong stirring 0.5 hour or more, ultrasound 2 after stirring~
4 hours, obtain evenly dispersed dispersion liquid；5~10ml silane guanidine reagents that second step obtains are slowly added in dispersion liquid, in room
The lower reaction of temperature stops reaction in 24~48 hours, obtains brown mixed liquor；After brown mixed liquor centrifuges under 10000r/min rotating speeds,
Thick product is obtained after being washed with absolute ethyl alcohol, deionized water, and pulverulent solids are obtained i.e. after thick product freeze-drying
For the guanidinated graphene oxide of fat.
4th step prepares fatty guanidinium ion graphene oxide
The guanidinated graphene oxide of 0.45g that third walks fat is dissolved in 300ml absolute ethyl alcohols, then it is added dropwise 5~
10ml bromination of n-butane is warming up to 80 DEG C, and 8~12 hours postcoolings of back flow reaction are to room temperature, by reactant in 10000r/min
It is centrifuged under rotating speed, with absolute ethyl alcohol, deionized water, respectively washing three times, obtains tan product, obtained after tan product freeze-drying
Powder solid is fatty guanidinium ion graphene oxide.
5th step, casting film
It dissolves a polymer in organic solvent, is stirred 3~5 hours at 55 DEG C, clear solution is obtained after being completely dissolved；Take
Fatty guanidinium ion graphene oxide that four steps obtain is added in clear solution, and room temperature continues after stirring 4~10 hours at ultrasound
Reason obtains uniform dispersion in 3~10 hours, and dispersion liquid is placed on glass plate and is formed a film, and 50 DEG C~80 DEG C stand 12 hours or more.
The polymer is polysulfones, polyphenylene oxide or polyether-ether-ketone；The organic solvent is DMAC N,N' dimethyl acetamide DMAC, diformazan
Base sulfoxide DMSO or 1-Methyl-2-Pyrrolidone NMP.The mass ratio of polymer and fatty guanidinium ion graphene oxide is 1：
0.15~0.35.
6th step, alkali process
Film obtained above is removed from glass pane surface, is placed in 1.0M aqueous slkalis and impregnates 24~48 hours, wash away film
The free ion in surface fully obtains fatty guanidinium ion graphene oxide doped type composite anion film after drying.
Beneficial effects of the present invention：1) easy to operate, environmental pollution is small, reaction condition is mild, preparation process is simple.2) from
Subbase is located at nanoparticle surface, is detached with main polymer chain, and the stability of film is improved from structure design.3) water in film contains
Amount increases the stability for being conducive to film.Be modified using silane reagent, with increasing for silane reagent amount, the water-retaining property of film and
Hydrophily increases；Water can be to the OH around guanidinium ion exchange base in film-" dilution " effect is generated, OH is reduced-Solvation journey
Degree, can play a certain protective role guanidinium ion exchange base, weaken OH-Attack to guanidinium ion exchange base.
Description of the drawings
The object construction figure of Fig. 1 composite anion films.
Fig. 2 is the infrared spectrum of fatty guanidinium ion graphene oxide.
Fig. 3 is the fatty guanidinium ion graphene oxide organo-mineral complexing alkaline membrane mode of appearance figure of doping, fatty guanidine from
It is 15% that sonization graphene oxide, which accounts for film quality score,.
Fig. 4 is the fatty guanidinium ion graphene oxide organo-mineral complexing alkaline membrane mode of appearance figure of doping, fatty guanidine from
It is 30% that sonization graphene oxide, which accounts for film quality score,.
Specific implementation mode
The preparation method and property for the compound anionic membrane that present invention be described in more detail by the following examples is related to
Energy.
Embodiment 1
In inert gas, at room temperature, tetramethylurea is dissolved in dichloromethane, oxalyl chloride is instilled with the speed of 2 drops/s, slowly
It is warming up to 60 DEG C to react 3 hours, removes solvent and obtain white solid, as Vilsmeyer salt, (tetramethylurea：Dichloromethane
Alkane：Oxalyl chloride=9ml：20ml：10.2ml)；
The Vilsmeyer salt of 1 molar part of preparation are taken to be dissolved in the 3- TSL 8330s of 1.5 molar parts,
80 DEG C are to slowly warm up to after being completely dissolved to react 24 hours.After completion of the reaction, it is the examination of silane guanidine to obtain rufous thick liquid
Agent.
0.5g graphene oxides are taken to be dissolved in 300ml absolute ethyl alcohols, strong stirring 1 hour, ultrasound 4 hours obtains uniformly
The dispersion liquid of dispersion is slowly added to 5ml silane guanidine reagents, reacts 24 hours and stops reaction, obtains brown mixed liquor, use is anhydrous
It is the guanidinated graphene oxide of fat that each centrifuge washing of ethyl alcohol, deionized water obtains pulverulent solids three times, after freeze-drying.
Above-mentioned steps (3) 0.45g products are dissolved in 300ml absolute ethyl alcohols, is added dropwise and 5ml bromination of n-butane is added, heating
To 80 DEG C, back flow reaction 8 hours is cooled to room temperature, three times using absolute ethyl alcohol, each centrifuge washing of deionized water, freeze-drying
After to obtain pulverulent solids be fatty guanidinium ion graphene oxide.
0.2g polysulfones is dissolved in the 1-Methyl-2-Pyrrolidone NMP of 5ml, is stirred 5 hours at 55 DEG C, after being completely dissolved
Clear solution is obtained, fatty guanidinium ion graphene oxide prepared by 0.03g steps (4) is added, continues stirring 4 hours, stirring
Ultrasound obtains uniform dispersion in 3 hours afterwards；It is 15 that fatty guanidinium ion graphene oxide, which accounts for polysulfones mass percent,.
By above-mentioned dispersion liquid casting film on a glass, at 60 DEG C dry 24 hours to get to compound anionic membrane.
By above-mentioned anionic membrane under glass plate gets on, immerses in 1M NaOH aqueous solutions 24 hours, be replaced as alkaline membrane.Fig. 1 is compound
The object construction figure of anionic membrane.Fig. 2 is the infrared spectrum of fatty guanidinium ion graphene oxide, and 2939 and 1471 go out in spectrogram
It is C=N absorption peaks for C-H absorption peaks, 1507,1125 be Si-O-C absorption peaks.Fig. 3 is the fatty guanidinium ion graphite oxide of doping
Alkene organo-mineral complexing alkaline membrane mode of appearance figure, it is 15% that fatty guanidinium ion graphene oxide, which accounts for film quality score,.
Embodiment 2
In inert gas, at room temperature, tetramethylurea is dissolved in dichloromethane, oxalyl chloride is instilled with the speed of 2 drops/s, slowly
It is warming up to 60 DEG C to react 3 hours, removes solvent and obtain white solid, as Vilsmeyer salt, (tetramethylurea：Dichloromethane
Alkane：Oxalyl chloride=9ml：30ml：10.4ml)；
The Vilsmeyer salt of 1 molar part of preparation are taken to be dissolved in the 3- TSL 8330s of 1.8 molar parts,
80 DEG C are to slowly warm up to after being completely dissolved to react 36 hours.After completion of the reaction, it is the examination of silane guanidine to obtain rufous thick liquid
Agent.
0.5g graphene oxides are taken to be dissolved in 300ml absolute ethyl alcohols, strong stirring 1 hour, ultrasound 4 hours obtains uniformly
The dispersion liquid of dispersion is slowly added to 6ml silane guanidine reagents, reacts 32 hours and stops reaction, obtains brown mixed liquor, use is anhydrous
It is the guanidinated graphene oxide of fat that each centrifuge washing of ethyl alcohol, deionized water obtains pulverulent solids three times, after freeze-drying.
Above-mentioned steps (3) 0.45g products are dissolved in 300ml absolute ethyl alcohols, is added dropwise and 6ml bromination of n-butane is added, heating
To 80 DEG C, back flow reaction 8 hours is cooled to room temperature, three times using absolute ethyl alcohol, each centrifuge washing of deionized water, freeze-drying
After to obtain pulverulent solids be fatty guanidinium ion graphene oxide.
0.2g polyphenylene oxide is dissolved in the 1-Methyl-2-Pyrrolidone NMP of 5ml, stirs 5 hours, is completely dissolved at 55 DEG C
After obtain clear solution, fatty guanidinium ion graphene oxide prepared by 0.04g steps (4) is added, continues stirring 4 hours, stirs
Ultrasound obtains uniform dispersion in 3 hours after mixing；It is 20 that fatty guanidinium ion graphene oxide, which accounts for polysulfones mass percent,.
By above-mentioned dispersion liquid casting film on a glass, at 60 DEG C dry 24 hours to get to compound anionic membrane.
By above-mentioned anionic membrane under glass plate gets on, immerses in 1M NaOH aqueous solutions 24 hours, be replaced as alkaline membrane.
Embodiment 3
In inert gas, at room temperature, tetramethylurea is dissolved in dichloromethane, oxalyl chloride is instilled with the speed of 2 drops/s, slowly
It is warming up to 60 DEG C to react 3 hours, removes solvent and obtain white solid, as Vilsmeyer salt, (tetramethylurea：Dichloromethane
Alkane：Oxalyl chloride=9ml：20ml：10.2ml)；
The Vilsmeyer salt of 1 molar part of preparation are taken to be dissolved in the 3- TSL 8330s of 2 molar parts, it is complete
80 DEG C are to slowly warm up to after fully dissolved to react 48 hours.After completion of the reaction, it is silane guanidine reagent to obtain rufous thick liquid.
0.5g graphene oxides are taken to be dissolved in 300ml absolute ethyl alcohols, strong stirring 1 hour, ultrasound 4 hours obtains uniformly
The dispersion liquid of dispersion is slowly added to 7ml silane guanidine reagents, reacts 32 hours and stops reaction, obtains brown mixed liquor, use is anhydrous
It is the guanidinated graphene oxide of fat that each centrifuge washing of ethyl alcohol, deionized water obtains pulverulent solids three times, after freeze-drying.
Above-mentioned steps (3) 0.45g products are dissolved in 300ml absolute ethyl alcohols, is added dropwise and 7ml bromination of n-butane is added, heating
To 80 DEG C, back flow reaction 8 hours is cooled to room temperature, three times using absolute ethyl alcohol, each centrifuge washing of deionized water, freeze-drying
After to obtain pulverulent solids be fatty guanidinium ion graphene oxide.
0.2g polysulfones is dissolved in the 1-Methyl-2-Pyrrolidone NMP of 5ml, is stirred 5 hours at 55 DEG C, after being completely dissolved
Clear solution is obtained, fatty guanidinium ion graphene oxide prepared by 0.05g steps (4) is added, continues stirring 4 hours, stirring
Ultrasound obtains uniform dispersion in 3 hours afterwards；It is 25 that fatty guanidinium ion graphene oxide, which accounts for polysulfones mass percent,.
By above-mentioned dispersion liquid casting film on a glass, at 60 DEG C dry 24 hours to get to compound anionic membrane.
By above-mentioned anionic membrane under glass plate gets on, immerses in 1M NaOH aqueous solutions 24 hours, be replaced as alkaline membrane.
Embodiment 4
In inert gas, at room temperature, tetramethylurea is dissolved in dichloromethane, oxalyl chloride is instilled with the speed of 2 drops/s, slowly
It is warming up to 60 DEG C to react 3 hours, removes solvent and obtain white solid, as Vilsmeyer salt, (tetramethylurea：Dichloromethane
Alkane：Oxalyl chloride=9ml：20ml：10.2ml)；
The Vilsmeyer salt of 1 molar part of preparation are taken to be dissolved in the 3- TSL 8330s of 1.5 molar parts,
80 DEG C are to slowly warm up to after being completely dissolved to react 24 hours.After completion of the reaction, it is the examination of silane guanidine to obtain rufous thick liquid
Agent.
0.5g graphene oxides are taken to be dissolved in 300ml absolute ethyl alcohols, strong stirring 1 hour, ultrasound 4 hours obtains uniformly
The dispersion liquid of dispersion is slowly added to 9ml silane guanidine reagents, reacts 48 hours and stops reaction, obtains brown mixed liquor, use is anhydrous
It is the guanidinated graphene oxide of fat that each centrifuge washing of ethyl alcohol, deionized water obtains pulverulent solids three times, after freeze-drying.
Above-mentioned steps (3) 0.45g products are dissolved in 300ml absolute ethyl alcohols, is added dropwise and 9ml bromination of n-butane is added, heating
To 80 DEG C, back flow reaction 8 hours is cooled to room temperature, three times using absolute ethyl alcohol, each centrifuge washing of deionized water, freeze-drying
After to obtain pulverulent solids be fatty guanidinium ion graphene oxide.
0.2g polyether-ether-ketones are dissolved in the 1-Methyl-2-Pyrrolidone NMP of 5ml, are stirred 5 hours at 55 DEG C, it is completely molten
Clear solution is obtained after solution, and fatty guanidinium ion graphene oxide prepared by 0.06g steps (4) is added, continues stirring 4 hours,
Ultrasound obtains uniform dispersion in 3 hours after stirring；It is 30 that fatty guanidinium ion graphene oxide, which accounts for polysulfones mass percent,.
By above-mentioned dispersion liquid casting film on a glass, at 60 DEG C dry 24 hours to get to compound anionic membrane.
By above-mentioned anionic membrane under glass plate gets on, immerses in 1M NaOH aqueous solutions 24 hours, be replaced as alkaline membrane.Fig. 4 is doping
Fatty guanidinium ion graphene oxide organo-mineral complexing alkaline membrane mode of appearance figure, fatty guanidinium ion graphene oxide account for film
Mass fraction is 30%.
Embodiment 5
In inert gas, at room temperature, tetramethylurea is dissolved in dichloromethane, oxalyl chloride is instilled with the speed of 2 drops/s, slowly
It is warming up to 60 DEG C to react 3 hours, removes solvent and obtain white solid, as Vilsmeyer salt, (tetramethylurea：Dichloromethane
Alkane：Oxalyl chloride=10ml：40ml：12ml)；
The Vilsmeyer salt of 1 molar part of preparation are taken to be dissolved in the 3- TSL 8330s of 1.5 molar parts,
80 DEG C are to slowly warm up to after being completely dissolved to react 24 hours.After completion of the reaction, it is the examination of silane guanidine to obtain rufous thick liquid
Agent.
0.5g graphene oxides are taken to be dissolved in 300ml absolute ethyl alcohols, strong stirring 1 hour, ultrasound 4 hours obtains uniformly
The dispersion liquid of dispersion is slowly added to 10ml silane guanidine reagents, reacts 48 hours and stops reaction, obtains brown mixed liquor, use nothing
It is the guanidinated graphite oxide of fat that each centrifuge washing of water-ethanol, deionized water obtains pulverulent solids three times, after freeze-drying
Alkene.
Above-mentioned steps (3) 0.45g products are dissolved in 300ml absolute ethyl alcohols, is added dropwise and 10ml bromination of n-butane is added, heating
To 80 DEG C, back flow reaction 8 hours is cooled to room temperature, three times using absolute ethyl alcohol, each centrifuge washing of deionized water, freeze-drying
After to obtain pulverulent solids be fatty guanidinium ion graphene oxide.
0.2g polysulfones is dissolved in the 1-Methyl-2-Pyrrolidone NMP of 5ml, is stirred 5 hours at 55 DEG C, after being completely dissolved
Clear solution is obtained, fatty guanidinium ion graphene oxide prepared by 0.07g steps (4) is added, continues stirring 4 hours, stirring
Ultrasound obtains uniform dispersion in 3 hours afterwards；It is 35 that fatty guanidinium ion graphene oxide, which accounts for polysulfones mass percent,.
By above-mentioned dispersion liquid casting film on a glass, at 60 DEG C dry 24 hours to get to compound anionic membrane.
By above-mentioned anionic membrane under glass plate gets on, immerses in 1M NaOH aqueous solutions 24 hours, be replaced as alkaline membrane.
Claims (8)
1. a kind of preparation method of fat guanidinium ion graphene oxide doped type composite anion film, which is characterized in that fat
Guanidinium ion graphene oxide doped type composite anion film is using polymer as main chain, with fatty guanidinium ion graphene oxide
Ionization reagent；Composite anion film is prepared in main chain and ionization reagent main chain and ionization reagent ultrasonic mixing；It is described
Polymer be polysulfones, polyphenylene oxide or polyether-ether-ketone；
The preparation method of the composite anion film, includes the following steps：
The first step prepares guanidine salt
Under inert conditions, tetramethylurea is dissolved in solvent A, then instills oxalyl chloride, reacted 1~10 hour at 60 DEG C, reacted
After remove solvent A, obtained white or pale yellow powder shape solid is guanidine salt；The tetramethylurea, solvent A, oxalyl chloride
Volume ratio be 1：2~10：1~1.2；
Second step prepares silane guanidine reagent
Under inert conditions, the guanidine salt that the first step obtains is dissolved in silane reagent, after stirring at normal temperature is completely dissolved to guanidine salt, is risen
Temperature to 80 DEG C react 24~48 hours, it is silane guanidine reagent to obtain rufous thick liquid；The guanidine salt, silane reagent
Molar ratio is 1：1.5~2；
Third walks, and prepares the guanidinated graphene oxide of fat
It takes 0.5g graphene oxides to be dissolved in 300ml absolute ethyl alcohols, is ultrasonically treated after strong stirring and obtains finely dispersed dispersion
Liquid；It is slowly added to 5~10ml silane guanidine reagents that second step obtains in dispersion liquid, is obtained after reacting 24~48 hours at room temperature
Brown mixed liquor；After the centrifugation of brown mixed liquor, wash with detergent, be freeze-dried after obtained pulverulent solids as fat guanidine
Base graphene oxide；
4th step prepares fatty guanidinium ion graphene oxide
The guanidinated graphene oxide of 0.45g fat that third walks is dissolved in 300ml absolute ethyl alcohols, 5~10ml bromines are added dropwise
For normal butane, after being reacted 8~12 hours under the conditions of 80 DEG C, it is cooled to room temperature, reactant centrifugation, detergent washing, freezing are dry
The powder solid obtained after dry is fatty guanidinium ion graphene oxide；
5th step, casting film
Polymer is added in organic solvent, the fatty guanidinium ion graphene oxide that the 4th step obtains, room temperature are added after dissolving
Stirring, supersound process obtain evenly dispersed dispersion liquid, and dispersion liquid is placed on glass plate and is formed a film, and 50 DEG C~80 DEG C standings 12 are small
When more than；The mass ratio of the polymer and fatty guanidinium ion graphene oxide is 1：0.15~0.35；
6th step, alkali process
The film that 5th step is obtained is removed from glass pane surface, is placed in aqueous slkali and is impregnated, and is washed away the free ion of film surface, is filled
Fatty guanidinium ion graphene oxide doped type composite anion film is obtained after dividing drying.
2. preparation method according to claim 1, which is characterized in that the solvent A described in the first step is toluene, dichloromethane
Alkane or ether.
3. preparation method according to claim 1 or 2, which is characterized in that the silane reagent described in second step is 3- ammonia
Base propyl trimethoxy silicane or 3-aminopropyltriethoxysilane.
4. preparation method according to claim 1 or 2, which is characterized in that second step, third step described in detergent be
Absolute ethyl alcohol or deionized water.
5. preparation method according to claim 3, which is characterized in that the detergent described in second step, third step is nothing
Water-ethanol or deionized water.
6. according to the preparation method described in claims 1 or 2 or 5, which is characterized in that the organic solvent described in the 5th step is N,
N- dimethylacetylamides DMAC, dimethyl sulfoxide (DMSO) DMSO or 1-Methyl-2-Pyrrolidone NMP.
7. preparation method according to claim 3, which is characterized in that the organic solvent described in the 5th step is N, N- diformazans
Yl acetamide DMAC, dimethyl sulfoxide (DMSO) DMSO or 1-Methyl-2-Pyrrolidone NMP.
8. preparation method according to claim 4, which is characterized in that the organic solvent described in the 5th step is N, N- diformazans
Yl acetamide DMAC, dimethyl sulfoxide (DMSO) DMSO or 1-Methyl-2-Pyrrolidone NMP.
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| CN104231294A (en) * | 2014-09-28 | 2014-12-24 | 中国科学技术大学 | Inorganic nano-composite anion exchange membrane and preparation method thereof |
| CN104835932A (en) * | 2015-04-28 | 2015-08-12 | 大连理工大学 | Preparation of organic-inorganic composite membrane and application thereof in alkaline fuel cell |
| CN104861188A (en) * | 2015-04-28 | 2015-08-26 | 大连理工大学 | Crosslinking type polymer anionic membrane and preparation method thereof |
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| CN104835932A (en) * | 2015-04-28 | 2015-08-12 | 大连理工大学 | Preparation of organic-inorganic composite membrane and application thereof in alkaline fuel cell |
| CN104861188A (en) * | 2015-04-28 | 2015-08-26 | 大连理工大学 | Crosslinking type polymer anionic membrane and preparation method thereof |
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