CN107452975A - A kind of alkaline membrane of the compound substance of liquid titanium containing dissociated ion and preparation method thereof - Google Patents

A kind of alkaline membrane of the compound substance of liquid titanium containing dissociated ion and preparation method thereof Download PDF

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CN107452975A
CN107452975A CN201710613864.4A CN201710613864A CN107452975A CN 107452975 A CN107452975 A CN 107452975A CN 201710613864 A CN201710613864 A CN 201710613864A CN 107452975 A CN107452975 A CN 107452975A
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ionic liquid
alkaline membrane
liquid
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weight
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朱红
陈跃楠
王芳辉
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Beijing University of Chemical Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1041Polymer electrolyte composites, mixtures or blends
    • H01M8/1046Mixtures of at least one polymer and at least one additive
    • H01M8/1048Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1041Polymer electrolyte composites, mixtures or blends
    • H01M8/1046Mixtures of at least one polymer and at least one additive
    • H01M8/1051Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1067Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1069Polymeric electrolyte materials characterised by the manufacturing processes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1069Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a kind of alkaline membrane of the compound substance of liquid titanium containing dissociated ion and preparation method thereof, belong to fuel cell alkaline anion-exchange membrane technical field, contain bromide PPO, triethylamine, ionic liquid and nano titanium oxide on described alkaline membrane main chain simultaneously, each component composition is as follows:In terms of the weight % of bromide PPO 100, the weight % of triethylamine 50 70, the weight % of ionic liquid 20 40, the weight % of nano titanium oxide 0.5 2.0.The ionic liquid of preparation is incorporated into quaternary ammonium cation type alkaline membrane by this method according to different proportion, is prepared for a series of ionic liquid composite membranes, and the ionic conductance of alkaline membrane is improved using " avtive spot " of ionic liquid offer in film.This polyphenylene oxide triethylamine ionic liquid nano titanium oxide alkaline membrane, there is excellent thermally and chemically stability, higher ionic conductance, and at high humidity, there is relatively low swelling, filming technology is simple, and morphotropism is small, the features such as high mechanical strength.

Description

A kind of alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter and its preparation Method
Technical field
It is more particularly to a kind of compound containing ionic liquid-titanium dioxide the present invention relates to a kind of alkaline membrane and preparation method thereof Alkaline membrane of thing and preparation method thereof, belong to fuel cell alkaline anion-exchange membrane technical field.
Technical background
Since 21 century, with the rapid development of technology and the rapid raising of living standards of the people, greatly improve People are to the demand of the energy, and fossil fuel is i.e. by depleted and its considerable damage to environment so that people are to new energy It is required that all the more urgent.Fuel cell (Fuel cells) is that one kind directly can efficiently turn chemical energy in fuel and oxidant The device (50%~70%) of electric energy is changed to, therefore there is good application prospect.Its advantages of is energy conversion efficiency height, is fired Material variation, noise is low, environment-friendly.2006, as emphasis in the scientific and technical important planning of State Council's issue One of R&D direction, fuel cell technology have been recognized as being preferred clean, efficient new energy power technology.Especially It is that Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cells (PEMFCs)) has been obtained for Extensive commercial applications are explored.
However, the critical material of Proton Exchange Membrane Fuel Cells:The cost and life-span of platinum catalyst and perfluoro sulfonic acid membrane are asked Topic becomes restriction, and it realizes commercialized important hindering factor.
Therefore, alkaline anion-exchange membrane fuel cell (anion exchange membrane fuel cells (AEMFCs)) because it can use non-precious metal catalyst in the basic conditions, have faster redox anti-in negative electrode Answer dynamics and of increased attention.Alkaline anion-exchange membrane (alkaline membrane) is alkaline anion-exchange membrane fuel The core component of battery.Preferable alkaline membrane is stable in the alkali that there is higher pH high ionic conductance to become reconciled with a temperature of Property and dimensional stability.However, in alkaline membrane the chemical stability of organic cation and skeleton become restrict its development Key factor.
Organic cation main at present has:Quaternary ammonium cation, glyoxaline cation, guanidinesalt cation, quaternary phosphonium cations, uncle Sulphur cation, and organometallic cation.However, in the basic conditions, Huffman drop easily occurs for these organic cations Solve the degraded such as (E2), nucleophilic displacement of fluorine (SN2), phosphorus Ye Lide (phosphorus ylides), ring open loop.
In order to avoid the generation of these degradeds, there is scientist to propose the cation using organometallic cation as alkaline membrane The chemical stability of alkaline kation improves in functional group.For example use:More coordination metal rhodium cations, crown ether cation etc.. But the stability for the metal rhodium cation being coordinated more is limited by the coordination stability of itself.It is anti-that de- coordination easily occurs in it Should.Na+, K+ are complexed to and are used to as alkaline kation be an extraordinary thinking in crown ether.But the alkali of this crown ether Property film when being worked under water environment conditions, the metal cation of crown ether complexing is easily lost in from crown ether so that alkaline membrane from Sub- conductivity reduces.
Ionic liquid refers to the liquid being composed entirely of ions, and most common form is organic cation and inorganic anion The salt collectively formed.Ionic liquid shows liquid at room temperature, has the advantages of many organic solvents institute is incomparable.Ion In liquid composition, common cation mainly has NR4+、PR4+, glyoxaline cation and pyrroles's salt ion etc., anion mainly includes X-、BF4-、PF6-Deng.In the last few years, ionic liquid was obtaining more and more extensive research due to its unique performance.Due to Ionic liquid is made up of the organic cation and inorganic anion of positively charged, therefore ionic liquid has certain ionic conduction energy Power.
Therefore, a kind of inorganic-organic composite material for the conductivity and mechanical performance that can improve alkaline membrane is developed, is used for The membrane material for meeting alkaline fuel cell work is prepared, by with very wide research and application prospect.
The content of the invention
An object of the present invention is to provide a kind of ionic liquid-composite titania material, mixes in alkaline membrane to make It is standby that there is excellent thermally and chemically stability, higher ionic conductance, and at high humidity, there is relatively low swelling, make Membrane process is simple, and morphotropism is small, alkaline membrane the features such as high mechanical strength.
The purpose of foregoing invention of the present invention, reaches by the following technical programs:
A kind of alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter, it is characterised in that:Described alkaline membrane master Contain bromide PPO, triethylamine, ionic liquid and nano titanium oxide on chain simultaneously, each component composition is as follows:With bromo The weight % of polyphenylene oxide 100 is counted, triethylamine 50-70 weight %, ionic liquid 20-40 weight %, nano titanium oxide 0.5-2.0 weight Measure %.
A kind of optimal technical scheme, it is characterised in that:In terms of the weight % of bromide PPO 100, the weight % of triethylamine 60, from The sub- weight % of liquid 30, the weight % of nano titanium oxide 1.
A kind of optimal technical scheme, it is characterised in that:The average grain diameter of described nano titanium oxide is 25 nanometers.
A kind of optimal technical scheme, it is characterised in that:The structure of polyphenylene oxide is in described bromide PPO:
A kind of optimal technical scheme, it is characterised in that:Described nano titanium oxide is the rutile structure of 25 nanometers of particle diameter Type.
A kind of optimal technical scheme, it is characterised in that:The free ionic liquid is(Me-IL)、(Eth-IL) or(HOEt-IL) one kind in.
It is a further object of the present invention to provide a kind of alkaline membrane of above-mentioned liquid containing dissociated ion-titanium dioxide compound matter Preparation method.
The above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of preparation method of the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter, it is comprised the following steps that:
(1) preparation of free ionic liquid
N-methyl imidazoles and iodomethane or bromoethane or bromoethanol are fed intake in single-necked flask, 2-3 hours are stirred at room temperature, Liquid in bottle gradually becomes white solid, after the completion of reaction, adds ethyl acetate washing, removes most ethyl acetate, Remaining solidliquid mixture revolving removes the ethyl acetate of residual, obtains white solid and (respectively obtains methyl ion liquid (Me- IL), ethyl ionic liquid (Eth-IL) and ethoxy ionic liquid (HOEt-IL));
(2) preparation of bromide PPO (BPPO)
Add appropriate polyphenylene oxide (PPO) in three-necked flask, add appropriate anhydrous carbon tetrachloride (or:Anhydrous four chlorination Carbon, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide, one or more of mixing of tetrahydrofuran are molten Agent) solvent is used as, in nitrogen atmosphere stirring and dissolving, after polyphenylene oxide is completely dissolved, add appropriate N- bromo-succinimides (NBS As bromine source) and benzoyl peroxide (BPO is as initiator), in nitrogen atmosphere back flow reaction, with methanol and dichloromethane weight Multiple wash crystallization, until methanol-water is no longer muddy during washing, the white-yellowish solid of completion will be washed, dry, it is hard to obtain quality White-yellowish solid (BPPO);
(3) preparation of alkaline membrane
White-yellowish solid obtained by step (2) is dissolved in DMA in proportion, at room temperature, magnetic force stirs Mix, be completely dissolved bromide PPO, after dissolving, triethylamine (TEA) is proportionally added into system, solution can be observed Color is gradually changed into brown from light yellow, and whole system is reacted at room temperature, then is proportionally added into nano titanium oxide thereto, Until titanium dioxide is uniformly dispersed in the solution, then is proportionally added into white solid obtained by step (1), will be molten after magnetic agitation Liquid stream is prolonged in super flat culture dish, is cast liquid forced air drying film forming at 80 DEG C, after film is taken off, is soaked in NaOH solution Row ion exchange certain time, after deionized water rinsing, that is, obtain alkaline membrane.
A kind of optimal technical scheme, it is characterised in that:White solid is respectively methyl ion liquid described in the step (1) Body (Me-IL), ethyl ionic liquid (Eth-IL) and ethoxy ionic liquid (HOEt-IL).
A kind of optimal technical scheme, it is characterised in that:The crystallization of repeated washing described in the step (2) is 3 times.
A kind of optimal technical scheme, it is characterised in that:The time of magnetic agitation described in the step (3) at room temperature is 4 hours.
A kind of optimal technical scheme, it is characterised in that:Whole system described in the step (3) is reacted 12 hours.
A kind of optimal technical scheme, it is characterised in that:The time of magnetic agitation described in the step (3) is 2 hours.
A kind of optimal technical scheme, it is characterised in that:Scattered use of nano titanium oxide described in the step (3) surpasses Sound.
A kind of optimal technical scheme, it is characterised in that:The concentration of NaOH solution described in the step (3) is 2mol L-1
Compared with prior art, the machine of the alkaline membrane containing ionic liquid-composite titania material prepared by the present invention Tool performance, thermo-chemical stability, ionic conductance lifting positive effect, and good stabilization is shown in the basic conditions Property, meet the requirement of fuel cell alkaline membrane at this stage.
Ionic liquid-composite titania material of the present invention, ionic liquid monomer is entrained in film and prepares composite membrane, Ionic liquid monomer is allowed to serve as " avtive spot " with ionic conductivity in ionic conduction in film, so, one Determine can to accelerate in degree the conduction of ion in film, so as to improve the ionic conductance of amberplex.
In the present invention, the titanium ion that titanium dioxide surface is not coordinated saturation plays a lewis acidic effect of electron deficient, Therefore can be interacted with other electron rich donors.And ionic liquid be made up of a kind of zwitterion it is organic Salt, so we can be inferred to by some reported in literature, the anionic group of ionic liquid and the table of nano titanium oxide Face has very strong suction-operated.Interaction and this interaction high temperature of the ionic liquid with nano titanium oxide surface When stability have been obtained for sufficiently studying, many documents demonstrate simultaneously in terms of experimental technique and theoretical method Self assembly of the electronegative ion on nano titanium oxide surface acts on.Therefore, we are acted on using this self assembly, effectively Reduce loss of the ionic liquid under high humidity environment, improve the concentration of ionic liquid in film, so that it is preferably sent out Wave the effect of assisting ion conduction.
The present invention is prepared for three kinds of different types of ionic liquids, and the ionic liquid of preparation is incorporated into according to different proportion In quaternary ammonium cation type alkaline membrane, a series of ionic liquid composite membranes are prepared for, " the active sites provided using ionic liquid in film Point " improves the ionic conductance of alkaline membrane.
The superiority of conductivity is improved based on ionic liquid-composite titania material, it is base that the present invention, which chooses polyphenylene oxide, This skeleton, by the way that triethylamine is loaded on polyphenyl ether skeleton, titanium dioxide is mixed in the organic solution of film, makes two by ultrasound The uniform branch of titanium oxide adds different ionic liquids in coating solution, allows ionic liquid absorption on titanium dioxide granule, Casting film-forming, alkalization, alkalization prepare corresponding alkaline membrane.
Below by the drawings and specific embodiments, the present invention is described in detail.It should be understood that described reality Apply example and only relate to the preferred embodiments of the invention, in the case of the spirit and scope of the present invention are not departed from, various composition and contain The changes and improvements of amount are all possible.
Brief description of the drawings
Fig. 1 is the film forming schematic flow sheet of the present invention.
Fig. 2-1 to Fig. 2-3 be the embodiment of the present invention 1 in synthesize three kinds of ionic liquids nucleus magnetic hydrogen spectrum (1HNMR), solvent From deuterated dimethyl sulfoxide (DMSO):Methyl ion liquid (Me-IL), ethyl ionic liquid (Eth-IL) or ethoxy ion Liquid (HOEt-IL).
Fig. 3-1 to Fig. 3-4 is that the embodiment of the present invention mixes three kinds of alkali that three kinds of ionic liquid-titanium dioxide granules are prepared into The nucleus magnetic hydrogen spectrum of property film and bromide PPO (1HNMR), solvent selects deuterated dimethyl sulfoxide (DMSO).
Fig. 4-1 to Fig. 4-3 is three that doping three kinds of ionic liquid-titanium dioxide granules of incorporation of the embodiment of the present invention are prepared into Ionic conductance-temperature variation of kind alkaline membrane.
Embodiment
Embodiment 1
Bromide PPO-methyl ion liquid-nano titanium oxide-triethylamine (Me-IL-TiO2- TEA) alkaline membrane system It is standby:
(1) preparation of methyl ion liquid (Me-IL)
By commercially available N-methyl imidazoles and iodomethane, according to mol ratio 1:1.2, feed intake in single-necked flask, 2-3 is stirred at room temperature Hour, the liquid in bottle gradually becomes white solid, after the completion of reaction, adds commercially available ethyl acetate, washs 0.5 hour, go The ethyl acetate of residual is evaporated off in 55 DEG C of backspins, obtains white solid for most ethyl acetate, remaining solidliquid mixture ;1HNMR is schemed as shown in Fig. 2-1, and its preparation process is as follows:
(2) preparation of bromide PPO (BPPO)
4 grams of commercially available polyphenylene oxide (PPO) are taken to be dissolved in 60 milliliters of commercial anhydrous carbon tetrachloride, at 60 DEG C, stirring and dissolving, dissolving 5.8 grams of commercially available N- bromosuccinamides and 0.29 gram of commercially available benzoyl peroxide (BPO is as initiator) are added afterwards, are heated to 80 DEG C, it is stirred at reflux 4 hours, yellow suspension is gradually converted into orange-yellow suspension, and after the completion of reaction, system is changed into blush and hanged Turbid, the blush suspension that reaction obtains is poured into the methanol solution for not stopping stirring and washed, it can be seen that product enters White-yellowish solid is immediately turned into after entering in methanol, methanol solution gradually becomes yellow-white solution, by obtained white-yellowish solid The methanol of face residual is extracted as far as possible, is put into appropriate commercially available dichloromethane and is dissolved, and glassy yellow is presented in solution, treats that solid is completely molten Solution, solution is transferred in 500ml revolving bottles, rotated at 48 DEG C, removes most of dichloromethane, until solution becomes very viscous It is thick, solution is poured into proper amount of methanol and washed again, repeats above-mentioned experimental procedure 3 times, until methanol-water is no longer during washing Muddiness, the white-yellowish solid completed will be washed, is put into 60 DEG C of oven dryings 12 hours, obtains scleroid white-yellowish solid bromine For 2 grams of polyphenylene oxide (BPPO), BPPO nucleus magnetic hydrogen spectrum (1HNMR Fig. 3-3) are seen, its preparation process is as follows:
(3) preparation of alkaline membrane
The bromide PPO (BPPO) of step (2) preparation after 0.3g drying is weighed in 100ml single-necked flasks, thereto Adding 8ml DMFs (DMF), sealing is stood afterwards, at room temperature, magnetic agitation 4 hours, is completely dissolved BPPO, Yellow transparent solution is obtained, after dissolving, it (is bromine equivalent to 0.181 gram to add 0.23ml triethylamines (TEA) into system For polyphenylene oxide quality 60.33%), solution colour can be observed and be gradually changed into brown from light yellow, whole system is at room temperature Reaction 12 hours, after completion of the reaction, titanium dioxide (the bromide PPO quality of 25 nanometers of 0.003g average grain diameters is added thereto 1%), at room temperature ultrasound 5 hours, make nano titanium oxide fully dispersed in a polymer solution, disperse after, thereto Add methyl ion liquid (Me-IL) prepared by 0.09g (the 30% of bromide PPO quality) steps (1), magnetic agitation 1 hour Afterwards, ultrasound 0.5 hour, obtains brown solution, and by solution curtain coating in super flat culture dish, curtain coating liquid is at 80 DEG C, forced air drying Film forming, nucleus magnetic hydrogen spectrum (1HNMR Fig. 3-1) is seen.
Note:In the present embodiment, bromide PPO-methyl ion liquid-nano titanium oxide-triethylamine (Me-IL- TiO2-TEA the mass ratio between) is, in terms of bromide PPO 100%:Triethylamine 60.33%, methyl ion liquid 30%, receives Rice titanium dioxide 1%.
By electrochemical workstation, polyphenylene oxide-methyl ion liquid-second of titanium dioxide-three is measured with AC impedence method Amine (Me-IL-TiO2- TEA) alkaline membrane ionic conductance, obtain its ionic conductance-temperature variation (σ-T) and see Fig. 4-1, After mixing nano titanium oxide and ionic liquid in film, the conductivity of film is obviously improved relative to pure film, illustrates nanometer Titanium dioxide-ionic liquid composite material can equally play a part of aiding in hydroxide ion conduction.Meanwhile in ionic liquid When concentration is identical, mix the composite membrane of nano titanium oxide have compared with the composite membrane ionic conductance for only adding ionic liquid it is aobvious The raising of work.During ionic liquid content 20% (using bromide PPO quality as reference), incorporation 1% is (with bromide PPO quality For reference) nano titanium oxide, the ionic conductance ratio of alkaline membrane improves 74.7% for maximum before incorporation, and ionic liquid contains When measuring 30%, 1% nano titanium oxide is mixed, the ionic conductance of alkaline membrane has reached 51.6mS/cm.Mix and receive in film After rice titanium dioxide, the nano titanium oxide and the methyl ion liquid that are dispersed in film form composite, and this is compound Material continues to play in film the effect of " avtive spot ", plays a part of assisting ion conduction.Meanwhile with nano titanium oxide After forming composite, the methyl ion liquid to dissociate in film is also stabilized, it is suppressed that their losses under high humidity environment, So that the ionic liquid of higher concentration is participated in assisting ion conduction, significantly carried so that the ionic conductance of film has It is high.
Embodiment 2
Bromide PPO-ethyl ion liquid-nanometer titanium dioxide-triethylamine (Eth-IL-TiO2- TEA) alkaline membrane Prepare:
(1) preparation of ethyl ionic liquid (Eth-IL)
By commercially available N-methyl imidazoles and bromoethane, according to mol ratio 1:1.2, feed intake in single-necked flask, 2-3 is stirred at room temperature Hour, the liquid in bottle gradually becomes white solid, after the completion of reaction, adds commercially available ethyl acetate, washs 0.5 hour, go The ethyl acetate of residual is evaporated off in 55 DEG C of backspins, obtains white solid for most ethyl acetate, remaining solidliquid mixture (ethyl ionic liquid), dry, it is stand-by;1HNMR is schemed as shown in Fig. 2-2, and its preparation process is as follows:
(2) preparation of bromide PPO (BPPO)
With embodiment 1;
(3) preparation of alkaline membrane
The bromide PPO (BPPO) of step (2) preparation after 0.3g drying is weighed in 100ml single-necked flasks, thereto After adding the commercially available DMFs of 8ml (DMF), sealing is stood, and at room temperature, magnetic agitation 4 hours, makes BPPO completely molten Solution, obtains yellow transparent solution, after dissolving, the commercially available triethylamines of 0.19ml (TEA) is added into system, solution can be observed Color is gradually changed into brown from light yellow, and whole system is reacted 12 hours, after completion of the reaction, added thereto at room temperature The commercially available nano titanium oxides of 0.003g (the 1% of bromide PPO quality), ultrasound 5 hours, fill nano titanium oxide at room temperature Disperse in a polymer solution, after disperseing, add 0.09g (the 30% of bromide PPO quality) step (1) thereto The ethyl ionic liquid of preparation, magnetic agitation ultrasound 0.5 hour, obtain brown solution, by solution curtain coating in super flat after 1 hour In culture dish, curtain coating liquid is at 80 DEG C, forced air drying, film forming.Nucleus magnetic hydrogen spectrum (1HNMR Fig. 3-2) is seen.
By electrochemical workstation, bromide PPO-ethyl base ion liquid-nanometer dioxy is measured with AC impedence method Change the ionic conductance of titanium-triethylamine (Eth-IL-TiO2-TEA) alkaline membrane, obtain its ionic conductance-temperature variation (σ- T) see Fig. 4-2, from figure we can see that:After mixing nano titanium oxide, the ionic conductance of composite membrane is compared with being not incorporated into Have before and be obviously improved, illustrate that nano titanium oxide equally plays a part of stable ethyl ionic liquid in film.It is compound The ionic conductance of film improves with the increase of ethyl ionic liquid content, illustrates that ionic liquid content is higher in film, auxiliary The ability of hydroxide ion conduction is stronger, therefore ionic conductance is also higher.
Embodiment 3
Bromide PPO-ethoxy ion liquid-nanometer titanium dioxide-triethylamine (HOEt-IL-TiO2- TEA) alkaline membrane Preparation:
(1) preparation of ethoxy ionic liquid (HOEt-IL)
By commercially available N-methyl imidazoles and bromoethanol, according to mol ratio 1:1.2, feed intake in single-necked flask, 2-3 is stirred at room temperature Hour, the liquid in bottle gradually becomes white solid, after the completion of reaction, adds commercially available ethyl acetate, washs 0.5 hour, go The ethyl acetate of residual is evaporated off in 55 DEG C of backspins, obtains white solid for most ethyl acetate, remaining solidliquid mixture (ethoxy ionic liquid), dry, it is stand-by;1HNMR schemes as Figure 2-3, and its preparation process is as follows:
(2) preparation of bromide PPO (BPPO)
With embodiment 1;
(3) preparation of alkaline membrane
The bromide PPO (BPPO) of step (2) preparation after 0.3g drying is weighed in 100ml single-necked flasks, thereto After adding the commercially available DMFs of 8ml (DMF), sealing is stood, and at room temperature, magnetic agitation 4h is completely dissolved BPPO, Obtain yellow transparent solution.After dissolving, the commercially available triethylamines of 0.27ml (TEA) are added into system, solution face can be observed Color is gradually changed into brown from light yellow, and whole system is reacted 12 hours at room temperature, after completion of the reaction, adds 0.003g thereto Commercially available nano titanium oxide (the 1% of bromide PPO quality), ultrasound 5 hours, make nano titanium oxide fully dispersed at room temperature In a polymer solution, after disperseing, 0.09g (the 30% of bromide PPO quality) ethoxy ionic liquid is added thereto Body, magnetic agitation ultrasound 0.5 hour, obtains brown solution after 1 hour, and by solution curtain coating in super flat culture dish, curtain coating liquid exists At 80 DEG C, forced air drying, film forming, nucleus magnetic hydrogen spectrum (1HNMR Fig. 3-3) is seen.
By electrochemical workstation, bromide PPO-ethoxy ion liquid-nanometer dioxy is measured with AC impedence method Change titanium-triethylamine (HOEt-IL-TiO2- TEA) alkaline membrane ionic conductance, obtain its ionic conductance-temperature variation (σ-T) is shown in Fig. 4-3, from figure we can see that:After mixing nano titanium oxide, the ionic conductance of composite membrane is not compared with mixing Have before entering and be obviously improved, illustrate that nano titanium oxide equally plays a part of stable ethoxy ionic liquid in film. The ionic conductance of composite membrane improves with the increase of ethoxy ionic liquid content, illustrates that ionic liquid content is got in film Height, the ability of auxiliary hydroxide ion conduction is stronger, therefore ionic conductance is also higher.This with methyl ion liquid and ethyl from The composite membrane rule of sub- liquid is consistent.
Embodiment 4
Other same as Example 3, difference is:
The anhydrous carbon tetrachloride of solvent of polyphenylene oxide is changed to N,N-dimethylformamide, dimethyl described in the step (2) Sulfoxide, DMAC N,N' dimethyl acetamide, one or more of mixed solvents of tetrahydrofuran.
(3) preparation of alkaline membrane
The bromide PPO (BPPO) of step (2) preparation after 0.3g drying is weighed in 100ml single-necked flasks, thereto After adding the commercially available DMFs of 8ml (DMF), sealing is stood, and at room temperature, magnetic agitation 4h is completely dissolved BPPO, Obtain yellow transparent solution.After dissolving, the commercially available triethylamines of 0.23ml (TEA) are added into system, solution face can be observed Color is gradually changed into brown from light yellow, and whole system is reacted 12 hours at room temperature, after completion of the reaction, adds 0.006g thereto Commercially available nano titanium oxide (the 2% of bromide PPO quality), ultrasound 5 hours, make nano titanium oxide fully dispersed at room temperature In a polymer solution, after disperseing, 0.12g (the 40% of bromide PPO quality) ethoxy ionic liquid is added thereto Body, magnetic agitation ultrasound 0.5 hour, obtains brown solution after 1 hour, and by solution curtain coating in super flat culture dish, curtain coating liquid exists At 80 DEG C, forced air drying, film forming.
Embodiment 5
Other same as Example 3, difference is:
The anhydrous carbon tetrachloride of solvent of polyphenylene oxide is changed to N,N-dimethylformamide, dimethyl described in the step (2) Sulfoxide, DMAC N,N' dimethyl acetamide, one or more of mixed solvents of tetrahydrofuran.
(3) preparation of alkaline membrane
The bromide PPO (BPPO) of step (2) preparation after 0.3g drying is weighed in 100ml single-necked flasks, thereto After adding the commercially available DMFs of 8ml (DMF), sealing is stood, and at room temperature, magnetic agitation 4h is completely dissolved BPPO, Obtain yellow transparent solution.After dissolving, the commercially available triethylamines of 0.23ml (TEA) are added into system, solution face can be observed Color is gradually changed into brown from light yellow, and whole system is reacted 12 hours, after completion of the reaction, added thereto at room temperature The commercially available nano titanium oxides of 0.0015g (the 0.5% of bromide PPO quality), ultrasonic 5h makes nano titanium oxide abundant at room temperature Disperse in a polymer solution, after disperseing, add 0.06g (the 20% of bromide PPO quality) ethoxy ion thereto Liquid, magnetic agitation ultrasound 0.5 hour, obtains brown solution after 1 hour, by solution curtain coating in super flat culture dish, is cast liquid At 80 DEG C, forced air drying, film forming.

Claims (10)

  1. A kind of 1. alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter, it is characterised in that:Described alkaline membrane main chain On contain bromide PPO, triethylamine, ionic liquid and nano titanium oxide simultaneously, each component composition is as follows:Gathered with bromo The weight % of phenylate 100 is counted, triethylamine 50-70 weight %, ionic liquid 20-40 weight %, nano titanium oxide 0.5-2.0 weight Measure %.
  2. 2. the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter as claimed in claim 1, it is characterised in that:Institute Contain bromide PPO, triethylamine, ionic liquid and nano titanium oxide, each component composition on the alkaline membrane main chain stated simultaneously It is as follows:In terms of the weight % of bromide PPO 100, the weight % of triethylamine 60, the weight % of ionic liquid 30, the weight of nano titanium oxide 1 Measure %.
  3. 3. the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter as claimed in claim 1 or 2, it is characterised in that: The ionic liquid is
  4. 4. the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter as claimed in claim 1 or 2, it is characterised in that: The nano titanium oxide is the rutile configuration of 25 nanometers of particle diameter.
  5. 5. the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter as claimed in claim 1 or 2, it is characterised in that: The structure of polyphenylene oxide in described bromide PPO is
  6. 6. the preparation method of the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter described in claim 1 or 2, Its step is as follows:
    (1) preparation of free ionic liquid
    One kind in N-methyl imidazoles and iodomethane, bromoethane, bromoethanol is fed intake in single-necked flask, it is small that 2-3 is stirred at room temperature When, the liquid in bottle gradually becomes white solid, after the completion of reaction, adds ethyl acetate washing, goes most acetic acid second Ester, remaining solidliquid mixture revolving remove the ethyl acetate of residual, obtain white solid;
    (2) preparation of bromide PPO
    Appropriate polyphenylene oxide is added in three-necked flask, adds appropriate solvent, in nitrogen atmosphere stirring and dissolving, polyphenylene oxide is completely dissolved Afterwards, appropriate N- bromo-succinimides and benzoyl peroxide are added, in nitrogen atmosphere back flow reaction, with methanol and dichloromethane Repeated washing crystallizes, until methanol-water is no longer muddy during washing, will wash the white-yellowish solid of completion, dries, obtains quality heavily fortified point Hard white-yellowish solid;
    (3) preparation of alkaline membrane
    White-yellowish solid obtained by step (2) is dissolved in DMA in proportion, at room temperature, magnetic agitation, made Bromide PPO is completely dissolved, and after dissolving, triethylamine is proportionally added into system, can be observed solution colour gradually by Light yellow to be changed into brown, whole system is reacted at room temperature, then is proportionally added into nano titanium oxide thereto, until titanium dioxide Titanium is uniformly dispersed in the solution, then is proportionally added into white solid obtained by step (1), after magnetic agitation, by solution curtain coating in super In flat culture dish, liquid forced air drying film forming at 80 DEG C is cast, after film is taken off, is soaked in NaOH solution and carries out ion exchange Certain time, after deionized water rinsing, that is, obtain alkaline membrane.
  7. 7. the preparation method of the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter as claimed in claim 6, it is special Sign is:White solid is respectively methyl ion liquid, ethyl ionic liquid and ethoxy ionic liquid described in the step (1) Body.
  8. 8. the preparation method of the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter as claimed in claim 6, it is special Sign is:The crystallization of repeated washing described in the step (2) is 3 times.
  9. 9. the preparation method of the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter as claimed in claim 6, it is special Sign is:The time of magnetic agitation described in the step (3) at room temperature is 4 hours, whole body described in the step (3) System's reaction 12 hours, the time of magnetic agitation described in the step (3) are 2 hours, nano-silica described in the step (3) Change the scattered of titanium and use ultrasound, the concentration of NaOH solution is 2molL described in the step (3)-1
  10. 10. the preparation method of the alkaline membrane of liquid containing dissociated ion-titanium dioxide compound matter as claimed in claim 6, its It is characterised by:Solvent described in the step (2) is anhydrous carbon tetrachloride, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), N, N- One or more of mixed solvents of dimethyl acetamide, tetrahydrofuran.
CN201710613864.4A 2017-07-25 2017-07-25 A kind of alkaline membrane of the compound substance of liquid titanium containing dissociated ion and preparation method thereof Pending CN107452975A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104130433A (en) * 2014-07-12 2014-11-05 太原理工大学 Preparation method of cross-linked polyphenyl ether composite proton exchange membrane
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
CN106147197A (en) * 2016-06-30 2016-11-23 北京化工大学 A kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104130433A (en) * 2014-07-12 2014-11-05 太原理工大学 Preparation method of cross-linked polyphenyl ether composite proton exchange membrane
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
CN106147197A (en) * 2016-06-30 2016-11-23 北京化工大学 A kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof

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YUHAO CHU,YUENAN CHEN等: "A new method for improving the ion conductivity of anion exchange membranes by using TiO2 nanoparticles coated with Ionic liquid", 《RSC ADVANCES》 *

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Application publication date: 20171208