CN107666003A - A kind of gas barrier and ionic conduction bi-functional thin-film material and preparation method thereof - Google Patents
A kind of gas barrier and ionic conduction bi-functional thin-film material and preparation method thereof Download PDFInfo
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- CN107666003A CN107666003A CN201710801612.4A CN201710801612A CN107666003A CN 107666003 A CN107666003 A CN 107666003A CN 201710801612 A CN201710801612 A CN 201710801612A CN 107666003 A CN107666003 A CN 107666003A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1055—Inorganic layers on the polymer electrolytes, e.g. inorganic coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention discloses a kind of gas barrier and ionic conduction bi-functional thin-film material and preparation method thereof.Methods described includes：It is stand-by that hydrotalcite nano piece is prepared first with hydro-thermal method, then chloromethylation and quaternized processing are carried out to polymer, laminated assembling technology is then used, by hydrotalcite nano piece and quaternary ammonium polymer composite membrane-forming, so that gas barrier and ionic conduction bi-functional thin-film material is made.Thin-film material obtained by the present invention has excellent gas barrier property, high ionic conductivity and good heat endurance.In addition, hydrotalcite wide material sources of the present invention；Hydrotalcite thin-film material is prepared simply, and cost is cheap, meets environmental requirement, is with a wide range of applications in fuel cell field.
Description
Technical field
The present invention relates to inorganic/organic hybrid films field of functional materials, and in particular to a kind of gas barrier passes with ion
Lead bi-functional thin-film material and preparation method thereof.
Background technology
With economic and society development, resource consumption rate is significantly increased on the earth, demand of the mankind to the energy
Also it is increasing.However, because fossil energy reserves are limited, therefore be badly in need of newly in the so rapid economic environment of energy resource consumption
The development and utilization of the energy, to solve increasingly serious energy crisis.Fuel cell technology exactly meets the tendency of in this case
And give birth to, and early in 19th century, just oneself warp produces very important effect to human society.
At present, polymer dielectric film fuel cell is divided into pem fuel according to the ion difference conducted in its film
Battery (PEMFC) and alkaline membrane cell (AEMFC).Wherein, E.I.Du Pont Company's Nafion membrane is ripe commercialized proton
Exchange membrane.By contrast, as AEMFC key components alkaline anion-exchange membrane development also in the starting stage, but because
There is the characteristics of high, the usable base metal electrode catalyst of electrode reaction activity, low-corrosiveness to turn into fuel cell field for it
Study hotspot.
In alkaline membrane cell (AEMFC), anion-exchange membrane, which plays, separates fuel and oxidant and conduction hydrogen-oxygen
The effect of radical ion.Wherein, ionic conductance is the performance for influenceing battery most critical, directly affects the efficiency of battery.Generally,
The ionic conductance of film can be improved by improving the IEC of ionomer.It has been found that IEC increase is often adjoint
Higher swelling behavior so that the mechanical performance and dimensional stability of film are deteriorated.However, add inorganic particle not only into film
Film mechanical performance can be improved, can also improve the water holding capacity of film.
Hydrotalcite (LDHs), it is the compound formed by interlayer anion and the accumulation of positively charged laminate, there is laminate gold
It is adjustable to belong to element ratio, the tradable feature of interlayer anion.Just because of LDH two-dimensional structure cause it possess it is higher from
Sub- exchange capacity, higher water absorbing capacity and relatively low swelling behavior, therefore be a kind of inorganic addition material of alkaline membrane well
Material, and the addition of hydrotalcite is it is also possible that film has higher gas barrier ability and heat endurance.
Therefore, the invention provides a kind of hydrotalcite thin-film material.
The content of the invention
Present invention seek to address that existing thin-film material water holding capacity for fuel cell is poor, heat endurance is poor, swellability
The technical problem that energy is high, gas barrier ability and ionic conductivity are poor, there is provided one kind has the dual work(of gas barrier/ionic conduction
Energy and the hydrotalcite thin-film material that good mechanical property, water holding capacity are strong, swelling behavior is low, heat endurance is strong.More specifically
Ground, the present invention provide a kind of preparation method of hydrotalcite thin-film material.
The technical scheme is that：It is stand-by that hydrotalcite nano piece is prepared first with hydro-thermal method, and then polymer is entered
Row chloromethylation and quaternized processing, it is then using laminated assembling technology, hydrotalcite nano piece and quaternary ammonium polymer is compound
Film forming, hydrotalcite thin-film material is finally made.
A kind of preparation method of hydrotalcite thin-film material of the present invention, comprises the following steps：
A. the mixing salt solution of solvable divalent metal salt and solvable trivalent metal salt is prepared；Prepare NaOH solution simultaneously；So
Mixing salt solution and sodium hydroxide solution are poured into full back-mixing rotating liquid-film reactor under 2000-4000rpm rotating speed afterwards
1-2min is blended, obtains white slurries；White slurries are positioned in autoclave and carry out crystallization, after cooling successively by centrifugation,
Washing, houghite colloidal solution is made；
B. polysulfones is dissolved in chloroform to form homogeneous phase solution, then adds trim,ethylchlorosilane and paraformaldehyde,
Butter of tin is added dropwise after stirring, then carries out back flow reaction, so that mixture is made；
C. mixture made from step B filtered, washed, dried with ethanol, white powder material is made；
D. white powder material step C obtained carries out quaternized processing, to obtain quaternary ammonium polymer solution；
E. clean PET substrate and dry at room temperature, to obtain the substrate handled well；
F. with the substrate handled well in the houghite colloidal solution soaking step E；One layer of hydrotalcite will be deposited afterwards
Substrate be placed in mass fraction be 2-10% quaternary ammonium polymer solution in soak 5-20min；
G. repeat step F, 0-100 times, you can gas barrier and ionic conduction bi-functional thin-film material is made.
Preferably, divalent metal M in described solvable divalent metal salt2+Selected from Co2+、Mg2+、Ni2+And Zn2+In
One kind, trivalent metal cation M in solvable trivalent metal salt3+Selected from Al3+And Fe3+In one kind.
Preferably, divalent metal M2+Concentration be 0.2-0.4mol/L, bivalent metal ion M2+With trivalent metal
Ion M3+Molar ratio range be 2-4, the concentration of NaOH solution is 0.15mol/L.
Preferably, in step, crystallization temperature is 90-120 DEG C；Crystallization time is 24-48h；
Preferably, in stepb, the quality of polysulfones is 7-15g, and the volume of chloroform is 400-800mL, trimethyl chlorine
The volume of silane is 20-44mL, and the quality of paraformaldehyde is 5-10g, and the volume of the butter of tin of dropwise addition is 0.2-0.4mL, is stirred
It is 30min to mix the time, and reflux time is 36-72h.
Preferably, in step D, the quaternized processing includes the white powder material that step C is obtained being dissolved in
In DMF, trimethylamine is added, 24-48h progress is stirred at room temperature, to obtain quaternary ammonium polymer solution；Its
The mol ratio of middle trimethylamine and the obtained white powder materials of step C is 3-5.
Preferably, in step E, it is cleaned by ultrasonic PET substrate with ethanol, acetone, water successively
10-30min, then substrate is cleaned up with deionized water.
Preferably, in step F, the time with the substrate handled well in houghite colloidal solution soaking step E is 5-
20min。
Described step A is replaced with：Prepare solvable divalent metal salt and the mixed liquor of solvable trivalent metal salt and urea；Will
The mixed liquor, which is positioned in autoclave, carries out crystallization, successively by centrifugation, washing, dry, obtained hydrotalcite precursor after cooling；
Then hydrotalcite precursor is configured to 0.15wt% houghite colloidal solution.
A kind of gas barrier and ionic conduction bi-functional thin-film material, the thin-film material is by any of the above-described preparation side
Obtained by method.
The beneficial effects of the invention are as follows：
1. the hydrotalcite colloid being prepared by the method for the present invention, there are different draw ratios and be rendered as nano-sheet
Structure, diffusion path of the gas molecule such as oxygen molecule in thin-film material can be extended as filler, and then can be improved
The gas barrier property of composite；And hydrotalcite can play conduction OH-Effect, improve composite ion pass
Lead performance.
2. due to the addition of hydrotalcite in the present invention so that the thin-film material has more preferable heat endurance, disclosure satisfy that it
Practical application.
3. obtained hydrotalcite thin-film material is characterized by XRD, SEM, TEM, it is good to show that the thin-film material has
Two-dimensional layered structure；By oxygen transit dose, ionic conduction, heat stability testing, show that the film has excellent oxygen
Barrier property, ionic conduction performance and thermal stability.
4th, hydrotalcite wide material sources of the present invention, cost are cheap；Hydrotalcite thin-film material is prepared simply, meets ring
Guaranteed request, it is with a wide range of applications in fuel cell field.
Brief description of the drawings
Fig. 1 is the XRD of the hydrotalcite sample obtained by the step A of the embodiment of the present invention 1；Wherein, abscissa 2Theta, it is single
Position：Degree, ordinate is intensity.
Fig. 2 is the SEM figures of the hydrotalcite sample obtained by the step A of the embodiment of the present invention 1.
Fig. 3 is the Tyndall effect figure of the hydrotalcite sample obtained by the step A of the embodiment of the present invention 1.
Fig. 4 is the SEM plans of hydrotalcite/polysulphone film sample obtained by the step G of the embodiment of the present invention 1.
Fig. 5 is the SEM sectional views of hydrotalcite/polysulphone film sample obtained by the step G of the embodiment of the present invention 1.
Fig. 6 is the thermal multigraph of hydrotalcite/polysulphone film sample obtained by the step G of the embodiment of the present invention 1.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Whole description, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
Embodiment 1：
A weighs 5.82g Co (NO3)2·6H2O and 3.75g Al (NO3)3·9H2O, which is dissolved in 100mL deionized waters, to be obtained
Mixing salt solution；The NaOH solution for weighing 2.4g simultaneously is dissolved in 400mL deionized waters, is stirred to clarify.Open full back-mixing rotation
Turn liquid film reactor, regulation rotating speed is 2000rpm, is then poured into mixing salt solution and sodium hydroxide solution simultaneously, rapidly anti-
Answer in device and be blended, white slurries are obtained after 1min.After white slurries are washed with deionized, it is transferred in autoclave, in 100 DEG C
Crystallization 16h, it is cooled to after room temperature successively by centrifugation, washing, you can obtain houghite colloidal solution.Wherein, Fig. 1 is shown
State the XRD of houghite colloidal solution；Fig. 2 shows the SEM figures of above-mentioned houghite colloidal solution；Fig. 3 shows above-mentioned neatly
The Tyndall effect figure of stone colloidal solution.From Figure 2 it can be seen that the micro-shape of hydrotalcite is presented as flaky nanometer structure, and have
Different draw ratios.It should be appreciated that the hydrotalcite colloid of flaky nanometer structure can extend gas molecule for example as filler
Diffusion path of the oxygen molecule in thin-film material, and then the gas barrier property of composite can be improved.In addition, hydrotalcite can
To play conduction OH-Effect, and then improve the ionic conduction performance of composite.
7g polysulfones is dissolved in 400mL chloroform solns by B, mechanical agitation at 50 DEG C, after forming homogeneous phase solution, adds
22mL trim,ethylchlorosilanes and 5g paraformaldehydes, after stirring 30min, 0.21mL butters of tin, back flow reaction 36h is added dropwise.
The mixture that C obtains step B filters, and is washed with ethanol, and drying obtains white powder material.
The obtained whitenesses of step C are dissolved in DMF solution by D, add trimethylamine solution, room
Temperature stirring 24h, quaternary ammonium polymer solution is obtained, the wherein mol ratio of trimethylamine and polymer is 3.
The PET substrate that thickness is 180 μm is cleaned by ultrasonic 10- by E with ethanol, acetone, water successively
30min, then substrate is cleaned up with deionized water, dried at room temperature；
The substrate handled well in step E is put into houghite colloidal solution after immersion 10min and taken out by F, uses deionized water
Rinse；The substrate that deposited one layer of hydrotalcite is placed in the quaternary ammonium polymer solution that mass fraction is 5% afterwards and soaked
10min, taking-up deionized water rinsing.
G repeat steps F30 times, it can obtain gas barrier and ionic conduction bi-functional thin-film material.
Fig. 4,5,6 respectively illustrate the SEM plans of the hydrotalcite composite obtained by embodiment 1, SEM sectional views
And thermal multigraph.From Fig. 4-6, the thin-film material has good two-dimensional layered structure and good heat endurance.In addition, through
Cross and oxygen transit dose, ionic conduction test are carried out to thin-film material, the oxygen transit dose for showing the film is 2.35cm3m-2day-1, ionic conductivity rate reaches 7.25mScm-1.That is, hydrotalcite film has excellent oxygen barrier property, ion
Conductive performance.
Embodiment 2：
A weighs 7.68g Mg (NO3)2·6H2O and 3.75g Al (NO3)3·9H2O, which is dissolved in 100mL deionized waters, to be obtained
Mixing salt solution, while the NaOH solution for weighing 2.4g is dissolved in 400mL deionized waters, is stirred to clarify；Open full back-mixing rotation
Turn liquid film reactor, regulation rotating speed is 3000rpm, is then poured into mixing salt solution and sodium hydroxide solution simultaneously, rapidly anti-
Answer in device and be blended, white slurries are obtained after 2min；After white slurries are washed with deionized, it is transferred in autoclave, in 110 DEG C
Crystallization 24h, it is cooled to after room temperature successively by centrifugation, washing, you can obtain houghite colloidal solution.
10g polysulfones is dissolved in 500mL chloroform solns by B, mechanical agitation at 50 DEG C, after forming homogeneous phase solution, adds
28.2mL trim,ethylchlorosilanes and 6.7g paraformaldehydes, after stirring 30min, 0.26mL butters of tin, back flow reaction 48h is added dropwise.
The mixture that C obtains step B filters, and is washed with ethanol, and drying obtains white powder material.
The white powder material that step C is obtained is dissolved in DMF solution by D, and it is molten to add trimethylamine
Liquid, 36h is stirred at room temperature, obtains quaternary ammonium polymer solution, the wherein mol ratio of trimethylamine and polymer is 4.
The PET substrate that thickness is 180 μm is cleaned by ultrasonic 10- by E with ethanol, acetone, water successively
30min, then substrate is cleaned up with deionized water, dried at room temperature；
The substrate handled well in step E is put into houghite colloidal solution after immersion 10min and taken out by F, uses deionized water
Rinse；The substrate that deposited one layer of hydrotalcite is placed in the quaternary ammonium polymer solution that mass fraction is 8% afterwards and soaked
10min, taking-up deionized water rinsing.
G repeat steps F50 times, it can obtain gas barrier and ionic conduction bi-functional thin-film material.
It should be pointed out that by being carried out to the structure and morphology of laminated film, oxygen barrier property, ionic conduction and heat endurance
Test, the results showed that：The oxygen transit dose of the film is 3.012cm3m-2day-1, ionic conductivity rate reaches 5.717mScm-1,
And it has good heat endurance.
Embodiment 3：
A weighs 5.82Co (NO3)2·6H2O and 1.875g Al (NO3)3·9H2O and 3.00g urea be dissolved in 100mL go from
Mixed solution is obtained in sub- water, mixed solution is sufficiently stirred, is transferred in autoclave, in 110 DEG C of thermostatic crystallization 24h, is cooled to
Successively by centrifuging, washing, dry after being washed with deionized after room temperature, you can obtain hydrotalcite precursor；
The houghite colloidal solution that the obtained hydrotalcite precursors of step A are configured to 0.15wt% by B is stand-by；
14.88g polysulfones is dissolved in 750mL chloroform solns by C, mechanical agitation at 50 DEG C, after forming homogeneous phase solution, adds
Enter 42mL trim,ethylchlorosilanes and 10g paraformaldehydes, after stirring 30min, 0.4mL butters of tin, back flow reaction 60h is added dropwise.
The mixture that D obtains step B filters, and is washed with ethanol, and drying obtains white powder material.
The white powder material that step C is obtained is dissolved in DMF solution by E, and it is molten to add trimethylamine
Liquid, 48h is stirred at room temperature, obtains quaternary ammonium polymer solution, the wherein mol ratio of trimethylamine and polymer is 5.
The PET substrate that thickness is 180 μm is cleaned by ultrasonic 10- by F with ethanol, acetone, water successively
30min, then substrate is cleaned up with deionized water, dried at room temperature；
The substrate handled well in step E is put into houghite colloidal solution after immersion 10min and taken out by G, uses deionized water
Rinse；The substrate that deposited one layer of hydrotalcite is placed in the polymer solution that mass fraction is 10% afterwards and soaks 10min, is taken
Go out to use deionized water rinsing.
H repeat steps G, 10 times, can obtain gas barrier and ionic conduction bi-functional thin-film material.
It should be pointed out that by being carried out to the structure and morphology of laminated film, oxygen barrier property, ionic conduction and heat endurance
Test, the results showed that：The oxygen transit dose of the film is 1.574cm3m-2day-1, ionic conductivity rate reaches 2.976mScm-1,
And it has good heat endurance.
The foregoing is only presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
All any modification, equivalent and improvement made within principle etc., should be included in the scope of the protection.Therefore,
Protection scope of the present invention described should be defined by scope of the claims.
Claims (10)
1. the preparation method of a kind of gas barrier and ionic conduction bi-functional thin-film material, it is characterised in that including following step
Suddenly：
A. the mixing salt solution of solvable divalent metal salt and solvable trivalent metal salt is prepared；Prepare NaOH solution simultaneously；Then will
Mixing salt solution and sodium hydroxide solution are poured into full back-mixing rotating liquid-film reactor and are blended under 2000-4000rpm rotating speed
1-2min, obtain white slurries；White slurries are positioned in autoclave and carry out crystallization, successively by centrifuging, washing after cooling,
Houghite colloidal solution is made；
B. polysulfones is dissolved in chloroform to form homogeneous phase solution, then adds trim,ethylchlorosilane and paraformaldehyde, stirring
After butter of tin is added dropwise, then carry out back flow reaction, be made mixture；
C. mixture made from step B filtered, washed, dried with ethanol, white powder material is made；
D. white powder material step C obtained carries out quaternized processing, to obtain quaternary ammonium polymer solution；
E. clean PET substrate and dry at room temperature, to obtain the substrate handled well；
F. with the substrate handled well in the houghite colloidal solution soaking step E；The base of one layer of hydrotalcite will be deposited afterwards
Bottom, which is placed in the quaternary ammonium polymer solution that mass fraction is 2-10%, soaks 5-20min；
G. repeat step F, 0-100 times, you can gas barrier and ionic conduction bi-functional thin-film material is made.
2. the preparation method of gas barrier according to claim 1 and ionic conduction bi-functional thin-film material, its feature
It is：Divalent metal M in described solvable divalent metal salt2+Selected from Co2+、Mg2+、Ni2+And Zn2+In one kind, can
Trivalent metal cation M in molten trivalent metal salt3+Selected from Al3+And Fe3+In one kind.
3. the preparation method of gas barrier according to claim 2 and ionic conduction bi-functional thin-film material, its feature
It is：Divalent metal M2+Concentration be 0.2-0.4mol/L, divalent metal M2+With trivalent metal cation M3+
Molar ratio range be 2-4, the concentration of NaOH solution is 0.15mol/L.
4. the preparation method of gas barrier according to claim 1 and ionic conduction bi-functional thin-film material, its feature
It is：In step, crystallization temperature is 90-120 DEG C；Crystallization time is 24-48h.
5. according to the preparation method of the gas barrier described in claim 1 and ionic conduction bi-functional thin-film material, it is special
Sign is：In stepb, the quality of polysulfones is 7-15g, and the volume of chloroform is 400-800mL, the body of trim,ethylchlorosilane
Product is 20-44mL, and the quality of paraformaldehyde is 5-10g, and the volume of the butter of tin of dropwise addition is 0.2-0.4mL, and mixing time is
30min, and reflux time are 36-72h.
6. according to the preparation method of the gas barrier described in claim 1 and ionic conduction bi-functional thin-film material, it is special
Sign is：In step D, the quaternized processing includes the white powder material that step C is obtained being dissolved in N, N- diformazans
In base formamide, trimethylamine is added, 24-48h progress is stirred at room temperature, to obtain quaternary ammonium polymer solution；Wherein trimethylamine
The mol ratio of the white powder material obtained with step C is 3-5.
7. according to the preparation method of the gas barrier described in claim 1 and ionic conduction bi-functional thin-film material, it is special
Sign is：In step E, it is cleaned by ultrasonic PET substrate 10- with ethanol, acetone, water respectively successively
30min, then substrate is cleaned up with deionized water.
8. according to the preparation method of the gas barrier described in claim 1 and ionic conduction bi-functional thin-film material, it is special
Sign is：In step F, the time with the substrate handled well in houghite colloidal solution soaking step E is 5-20min.
9. the system of the gas barrier and ionic conduction bi-functional thin-film material according to any claim in claim 1
Preparation Method, it is characterised in that replace with the step A in claim 1：Prepare solvable divalent metal salt and solvable trivalent metal
The mixed liquor of salt and urea；The mixed liquor is positioned in autoclave and carries out crystallization, successively by centrifuging, washing, dry after cooling
It is dry, hydrotalcite precursor is made；Then hydrotalcite precursor is configured to 0.15wt% houghite colloidal solution.
10. a kind of gas barrier and ionic conduction bi-functional thin-film material, it is characterised in that the thin-film material is according to power
Profit is required made from the method in 1-9 described in any claim.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585888A (en) * | 2018-11-07 | 2019-04-05 | 大连理工大学 | A kind of blending type anion-exchange membrane and preparation method thereof |
| CN109817999A (en) * | 2019-01-23 | 2019-05-28 | 西北工业大学 | Silver catalysis magnalium laminar hydroxide film formates fuel cell and preparation method |
| CN110433673A (en) * | 2019-07-08 | 2019-11-12 | 淮阴师范学院 | A kind of quaternary ammonium salt functionalization polysulfones-nano-attapulgite stone hybrid anion exchange membrane and preparation method thereof |
| CN112928322A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Hydrotalcite in-situ growth composite membrane and preparation method and application thereof |
| CN112928315A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Preparation and application of composite membrane for alkaline zinc-based flow battery |
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2017
- 2017-09-07 CN CN201710801612.4A patent/CN107666003B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585888A (en) * | 2018-11-07 | 2019-04-05 | 大连理工大学 | A kind of blending type anion-exchange membrane and preparation method thereof |
| CN109817999A (en) * | 2019-01-23 | 2019-05-28 | 西北工业大学 | Silver catalysis magnalium laminar hydroxide film formates fuel cell and preparation method |
| CN109817999B (en) * | 2019-01-23 | 2022-04-08 | 西北工业大学 | Silver-catalyzed magnalium layered hydroxide membrane formate fuel cell and preparation method thereof |
| CN110433673A (en) * | 2019-07-08 | 2019-11-12 | 淮阴师范学院 | A kind of quaternary ammonium salt functionalization polysulfones-nano-attapulgite stone hybrid anion exchange membrane and preparation method thereof |
| CN110433673B (en) * | 2019-07-08 | 2021-02-12 | 淮阴师范学院 | Quaternary ammonium salt functionalized polysulfone-nano attapulgite hybrid anion-exchange membrane and preparation method thereof |
| CN112928322A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Hydrotalcite in-situ growth composite membrane and preparation method and application thereof |
| CN112928315A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Preparation and application of composite membrane for alkaline zinc-based flow battery |
| CN112928315B (en) * | 2019-12-06 | 2022-09-16 | 中国科学院大连化学物理研究所 | Preparation and application of composite membrane for alkaline zinc-based flow battery |
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