CN106025316A - Anion exchange membrane and preparation method therefor - Google Patents
Anion exchange membrane and preparation method therefor Download PDFInfo
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- CN106025316A CN106025316A CN201610470877.6A CN201610470877A CN106025316A CN 106025316 A CN106025316 A CN 106025316A CN 201610470877 A CN201610470877 A CN 201610470877A CN 106025316 A CN106025316 A CN 106025316A
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- Prior art keywords
- exchange membrane
- anion exchange
- metal hydroxides
- preparation
- nanometer sheet
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses an anion exchange membrane and a preparation method therefor. The membrane takes a metal hydroxide nanosheet as the base material; the chemical general formula of the metal hydroxide nanosheet is [M<2+><1-x>M<3+><x>(OH)<2>]<x+>[A<n-><x/n>.<z>H<2>O], wherein M<2+> and M<3+> are divalent metal cations and trivalent metal cations respectively; and A<n-> are anions which can stably exist in an alkali solution. The preparation method for the anion exchange membrane comprises the following two steps of (1) synthesizing the metal hydroxide nanosheet; and (2) casting the metal hydroxide nanosheet into the membrane. Compared with the metal hydroxide with a multilayer stacked structure, the metal hydroxide with the two-dimensional structure has relatively low constraint on the anions; namely, the anions are higher in migration capability, so that the anion exchange membrane with higher conductivity can be obtained; in addition, the metal hydroxide nanosheet does not contain a quaternary amine group which is utilized by most of anions, so that the problem of degradation of the quaternary amine group in a high-temperature strong-alkali environment is avoided; the anion exchange membrane obtains high stability; and finally, the preparation method for the anion exchange membrane is simple and easy to implement; and the utilization of a large amount of highly toxic organic solvent is avoided.
Description
Technical field
The present invention relates to technical field of membrane, in particular, relate to a kind of anion exchange membrane and preparation method thereof.
Background technology
It is low that alkaline anion-exchange membrane fuel cell (AEMFC) has hydrogen reduction overpotential, fast prominent excellent of electrode reaction kinetics
Point, the working environment of alkalescence is that non-precious metal catalyst creates good condition simultaneously.But alkaline anion-exchange membrane combustion at present
It is low that material battery still suffers from membrane conductivity, the problem that stability is low.
Anion exchange membrane (AEM) is the core component of AEMFC, and it directly influences the energy conversion efficiency of fuel cell and makes
Use the life-span.Up to the present, the preparation method of AEM is mainly by some polymeric matrixs are carried out chemical modification process, bag
Include chloromethylation, quaternized or imidazoles etc..Wherein, chloromethylation process generally requires the reagent using severe toxicity carcinogenecity, and
Membrane structure may be caused damage or the phenomenon that chloromethylation is uneven occurs by chloromethylation reagents, and the performance causing film is unstable
Fixed；Quaternized AEM conduction is excellent, but the stabilized operating temperature the highest under alkaline environment of quaternary ammonium group is only 60 DEG C, such as Kreuer
Et al. the report of (Chemistry of Materials, 2014.26 (1): 361-380), this hinders the business-like process of AEM significantly；
And the AEM of imidazoles is under the conditions of high temperature low humidity or high pH, imidazole ring is easily degraded, and reduces the life-span of AEMFC.
Separately have been reported that it is to utilize tabletting method to prepare AEM.As Tadanaga etc. (Adv Mater, 2010.22 (39): p.4401-4404) will
Metal hydroxides pressed powder prepares the report of AEM.But the technique of this tabletting masking also exists porous, thickness is big, towards chi
Very little little, electrical conductivity is low waits limitation.
Summary of the invention
In order to solve the problems of the prior art, the present invention provides a kind of anion exchange membrane and preparation method thereof, solves existing skill
AEM electrical conductivity and the best problem of stability in art.
The technical scheme is that a kind of anion exchange membrane, described film with metal hydroxides nanometer sheet as substrate building,
The chemical general formula of described metal hydroxides nanometer sheet is: [M2+ 1-xM3+ x(OH)2]x+[An- x/n·zH2O], wherein M2+And M3+It is respectively
Bivalence and trivalent metal cation, An-For in alkaline solution can the anion of stable existence, n is the integer of more than 1, and x is
0.1-0.4, z are more than 0.
A kind of preparation method of anion exchange membrane, including following two steps:
(1) synthesis metal hydroxides nanometer sheet；
(2) metal hydroxides nanometer sheet is cast film.
The chemical general formula of described metal hydroxides nanometer sheet is: [M2+ 1-xM3+ x(OH)2]x+[An- x/n·zH2O], wherein M2+And M3+
It is respectively bivalence and trivalent metal cation, An-For in alkaline solution can the anion of stable existence, n is the integer of more than 1, x
It is more than 0 for 0.1-0.4, z.
The method of described step (1) synthesis metal hydroxides nanometer sheet is: metal precursor and alkalization reagent are dissolved in H2O2
In, ultrasonic, obtain solution A；Solution A moves into polytetrafluoroethyllining lining reactor, and specified temp lower seal reacts, reaction
After end, obtain the solution of metal hydroxides nanometer sheet.Described alkalization reagent is carbamide, the one in hexamethylenetetramine；
Metal precursor and alkalization reagent molar ratio are 2:5；Specified temp is the arbitrary temperature in 120-200 DEG C.
The method of described step (1) synthesis metal hydroxides nanometer sheet can also be: metal hydroxides is dispersed in Methanamide
In, supersound process 10min-48h, available metal hydroxides nanometer sheet solution.
The method of described step (1) synthesis metal hydroxides nanometer sheet can also be: is dissolved in water by metal precursor, with ammonia
Aqueous solution, pH regulates and controls in the range of 8-12, stirs, be centrifuged subsequently under nitrogen atmosphere, washing, then is centrifuged, water
Wash, repeat this circulation, product will be centrifuged for the last time be distributed in water the solution of available metal hydroxides nanometer sheet.
The method of described step (1) synthesis metal hydroxides nanometer sheet can also be: metal hydroxides is distributed to short chain alcohol
Middle heat treatment, obtains the solution of metal hydroxides nanometer sheet.
The method of described step (1) synthesis metal hydroxides nanometer sheet can also be: utilizes coprecipitation method to synthesize metal hydrogen-oxygen
Compound, before metal hydroxides is dried, " wet cake " after filtering is distributed in acetone, after stirring 1-2 hour, filter
This sample is also washed with acetone, dried available metal hydroxides nanometer sheet.
It is casting method, spin-coating method, Filtration, gas-liquid circle that metal hydroxides nanometer sheet is cast the method for film by described step (2)
One in the construction from part of face.
The invention has the beneficial effects as follows:
(1) obtain compared with metal hydroxides or the higher electrical conductivity of polymer/metal hydroxide composite material AEM.Because
In metal hydroxides nanometer sheet, object anion has broken away from the part constraint of narrow interlayer, will have bigger mobility, and then
Obtain the higher AEM of electric conductivity.
(2) heat stability is high.Inorganic metal hydroxide is not related to the quaternary amines that most AEM is utilized, can be fundamentally
Avoid the problem that AEM quaternary amine base is degraded.
(3) preparation method of AEM of the present invention is simple, meets the theory of Green Chemistry.
Accompanying drawing explanation
Fig. 1 is Mg3Al-CO3Metal hydroxides and Mg3Al-CO3The X-ray diffractogram of metal hydroxides nanometer sheet AEM；
It is Mg that upper right embeds figure3Al-CO3X-ray diffractogram after the amplification of metal hydroxides nanometer sheet AEM；
Fig. 2 is Mg3Al-CO3Metal hydroxides and Mg3Al-CO3The weight-loss curve figure of metal hydroxides nanometer sheet AEM；
Fig. 3 is Mg3Al-CO3Metal hydroxides and Mg3Al-CO3Metal hydroxides nanometer sheet AEM electricity at different temperatures
Conductance figure.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
Mg3Al-CO3The synthesis of hydroxide nano sheet AEM
Ultrasonic 30min after magnesium nitrate, aluminum nitrate, carbamide and hydrogen peroxide are mixed together, the solution being uniformly mixed, name
For solution A, wherein magnesium ion and aluminum ions mol ratio are 3:1, and carbamide and aluminum ions mol ratio are 10:1, hydrogen peroxide
Mass fraction elects 30% as.
Solution A is reacted at a temperature of 150 DEG C 24h, and reaction terminates the cooling of rear Temperature fall and obtains Mg3Al-CO3Hydroxide is received
Rice sheet solution, by solution under the pressure of 1Kg room temperature in vacuo filter 1h, washing several times, take off filter membrane, by filter membrane together with
Filter cake drying at room temperature together, takes off filter cake from filter membrane after drying, obtains Mg3Al-CO3Hydroxide nano sheet AEM.
Embodiment 2
Zn3Al-CO3The synthesis of hydroxide nano sheet AEM
Ultrasonic 30min after zinc nitrate, aluminum nitrate, carbamide and hydrogen peroxide are mixed together, the solution being uniformly mixed, name
For solution A, wherein zinc ion and aluminum ions mol ratio are 3:1, and carbamide and aluminum ions mol ratio are 10:1, hydrogen peroxide
Mass fraction elects 30% as.
Solution A is preferably reacted at a temperature of 150 DEG C 30h, and reaction terminates the cooling of rear Temperature fall and obtains Zn3Al-CO3Hydroxide
Thing nanometer sheet solution, filters 1h by solution room temperature in vacuo under the pressure of 1Kg, and washing several times, takes off filter membrane, by filter membrane
Together with filter cake drying at room temperature, after drying filter cake is taken off from filter membrane, obtain Zn3Al-CO3Hydroxide nano sheet AEM.
Embodiment 3
Co2The synthesis of Al-Cl hydroxide nano sheet AEM
Cobaltous chloride, aluminum chloride, carbamide are dissolved in deionized water, total concentration be the concentration of 50mM. three than for 2:1:7, with
After by this solution move into reactor, at 100 DEG C react 24h. obtain Co2Al-CO3Hydroxide.Take the above-mentioned synthesis of 0.5g
Co2Al-CO3Hydroxide is distributed in the NaCl HCl mixed solution (1M NaCl and 3.3mM HCl) of 500mL, nitrogen
Atmosphere encloses lower stirring 24h, obtains Co2Al-Cl hydroxide；Weigh 0.1g Co2Al-Cl hydroxide is dispersed in 100mL
In Methanamide, stir 2 days under blanket of nitrogen, obtain Co2Al-Cl hydroxide nano sheet solution；The Co that will obtain2Al-Cl hydrogen-oxygen
Compound nanometer sheet solution-cast, in electro-conductive glass substrate, is dried to obtain Co2Al-Cl hydroxide nano sheet AEM.
Embodiment 4
Mg2Al-NO3The synthesis of metal hydroxides nanometer sheet AEM
5.13g magnesium nitrate, 3.75g aluminum nitrate being dissolved in the deionized water of 100mL, named solution A, by solution
Ammonia (25 28wt%) solution of A Yu 80mL is added simultaneously in flask, stirs under blanket of nitrogen, the pH control of reaction system
System is about 10, by mixed liquor high speed centrifugation after 10min, and washing, then be centrifuged, washing, repeat this circulation, by last
Secondary centrifugal product is distributed in water the solution of available metal hydroxides nanometer sheet；By Mg2Al-NO3Metal hydroxides nanometer sheet
Solution water-bath at 85 DEG C, the gas-liquid interface at solution can get the Mg of self assembly2Al-NO3Metal hydroxides nanometer sheet
AEM。
Embodiment 5
Mg3Al-CO3The synthesis of metal hydroxides
Ultrasonic vibration, wherein, magnesium ion and aluminum ions mole is carried out after magnesium nitrate, aluminum nitrate, carbamide and deionized water being mixed
Ratio is 3:1, and carbamide and aluminum ions mol ratio are 10:1, the named solution A of solution obtained after concussion,；Solution A is moved into
Reactor, reacts 30h at a temperature of 120 DEG C, and reaction terminates the cooling of rear Temperature fall and obtains Mg3Al-CO3Metal hydroxides
Precipitation, filters precipitation, and washing several times, is drying to obtain Mg3Al-CO3Metal hydroxides.
The above is only the preferred embodiment of the present invention, it is noted that for those skilled in the art,
Under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should be regarded as this
Bright protection domain.
Claims (10)
1. an anion exchange membrane, it is characterised in that described film with metal hydroxides nanometer sheet as substrate building, described metallic hydrogen
The chemical general formula of oxide nano-slice is: [M2+ 1-xM3+ x(OH)2]x+[An- x/n·zH2O], wherein M2+And M3+Be respectively bivalence and
Trivalent metal cation, An-For in alkaline solution can the anion of stable existence, n is the integer of more than 1, and x is 0.1-0.4,
Z is more than 0.
2. the preparation method of an anion exchange membrane, it is characterised in that include following two steps:
(1) synthesis metal hydroxides nanometer sheet；
(2) metal hydroxides nanometer sheet is cast film.
The preparation method of anion exchange membrane the most according to claim 2, it is characterised in that described metal hydroxides nanometer sheet
Chemical general formula is: [M2+ 1-xM3+ x(OH)2]x+[An- x/n·zH2O], wherein M2+And M3+It is respectively bivalence and trivalent metal cation,
An-For in alkaline solution can the anion of stable existence, n is the integer of more than 1, x be 0.1-0.4, z be more than 0.
The preparation method of anion exchange membrane the most according to claim 2, it is characterised in that described step (1) synthesis metallic hydrogen
The method of oxide nano-slice is: metal precursor and alkalization reagent are dissolved in H2O2In, ultrasonic, obtain solution A；Will
Solution A moves into polytetrafluoroethyllining lining reactor, and specified temp lower seal reacts, and after reaction terminates, obtains metallic hydrogen oxidation
The solution of thing nanometer sheet.
The preparation method of anion exchange membrane the most according to claim 2, it is characterised in that described step (1) neutral and alkaliization is tried
Agent is carbamide, the one in hexamethylenetetramine；Metal precursor and alkalization reagent molar ratio are 2:5；Specified temp is
Arbitrary temperature in 120-200 DEG C.
The preparation method of anion exchange membrane the most according to claim 2, it is characterised in that described step (1) synthesis metallic hydrogen
The method of oxide nano-slice is: be dispersed in Methanamide by metal hydroxides, supersound process 10min-48h, can obtain
To metal hydroxides nanometer sheet solution.
The preparation method of anion exchange membrane the most according to claim 2, it is characterised in that described step (1) synthesis metallic hydrogen
The method of oxide nano-slice is: is dissolved in water by metal precursor, mixes with ammonia spirit, and pH regulates and controls to 8-12 model
In enclosing, stir under nitrogen atmosphere, be centrifuged subsequently, washing, then be centrifuged, washing, repeat this circulation, by last
Secondary centrifugal product is distributed in water the solution of available metal hydroxides nanometer sheet.
The preparation method of anion exchange membrane the most according to claim 2, it is characterised in that described step (1) synthesis metallic hydrogen
The method of oxide nano-slice is: metal hydroxides is distributed to heat treatment in short chain alcohol, obtains metal hydroxides nanometer
The solution of sheet.
The preparation method of anion exchange membrane the most according to claim 2, it is characterised in that described step (1) synthesis metallic hydrogen
The method of oxide nano-slice is: utilize coprecipitation method to synthesize metal hydroxides, before metal hydroxides is dried, and will
" wet cake " after filtration is distributed in acetone, after stirring 1-2 hour, and, filter this sample and wash with acetone, after drying may be used
Obtain metal hydroxides nanometer sheet.
The preparation method of anion exchange membrane the most according to claim 2, it is characterised in that described step (2) is by metal hydrogen-oxygen
It is the one in casting method, spin-coating method, Filtration, gas-liquid interface construction from part that compound nanometer sheet casts the method for film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107910575A (en) * | 2017-11-19 | 2018-04-13 | 湖南辰砾新材料有限公司 | One kind is based on hexamethylene tetramine salt anion-exchange membrane and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107910575A (en) * | 2017-11-19 | 2018-04-13 | 湖南辰砾新材料有限公司 | One kind is based on hexamethylene tetramine salt anion-exchange membrane and preparation method thereof |
| CN107910575B (en) * | 2017-11-19 | 2020-03-27 | 湖南辰砾新材料有限公司 | Anion exchange membrane based on hexamethylenetetramine salt and preparation method thereof |
| CN111276725A (en) * | 2017-11-19 | 2020-06-12 | 湖南辰砾新材料有限公司 | Anion exchange membrane fuel cell |
| CN111276725B (en) * | 2017-11-19 | 2021-10-08 | 湖南辰砾新材料有限公司 | Anion exchange membrane fuel cell |
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Application publication date: 20161012 |