CN106496617A - A kind of crosslinked polyethers ether ketone high temperature proton-conductive films and preparation method thereof - Google Patents
A kind of crosslinked polyethers ether ketone high temperature proton-conductive films and preparation method thereof Download PDFInfo
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Abstract
The application belongs to battery material technical field, it is related to a kind of crosslinked polyethers ether ketone high temperature proton-conductive films and preparation method thereof, more particularly to a kind of inorganic oxide nanoparticles of Ionic Liquid Modified and the proton-conductive films of sulfonated polyether-ether-ketone crosslinking and preparation method thereof.Material disclosed in this invention and high temperature proton-conductive films are comprising inorganic oxide nanoparticles and the sulfonated polyether-ether-ketone through Ionic Liquid Modified.Conduction membrane material provided by the present invention can rely on water as transmitting medium under normal temperature condition, under the high temperature conditions by ionic liquid as proton conductive medium, different temperature ranges, stable performance is can adapt to, can be widely applied to prepare the Proton Exchange Membrane Fuel Cells (PEMC) for being applied to different temperatures scope.Preparation method synthesis technique operating procedure disclosed in this invention is simple, and the conductive membranes for preparing have higher conductivity, stable performance under the high temperature conditions.
Description
Technical field
The invention belongs to battery material technical field, is related to a kind of crosslinked polyethers ether ketone high temperature proton-conductive films and its preparation
Method, more particularly to the proton that a kind of inorganic oxide nanoparticles of Ionic Liquid Modified are crosslinked with sulfonated polyether-ether-ketone
Conductive membranes and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell, PEMFC) is because of its energy
High conversion efficiency, quick start, pollution-free and infra-red radiation and lead in traffic power source, portable power supplies and stationary electric power plant power supply
Domain is with a wide range of applications.A major obstacle for hindering PEMFC practical is its high cost, its major embodiment
In its perfluorinated sulfonic acid proton-conductive films of needs using water as transmitting medium, noble metal catalyst and comprising humidifier and radiating
The numerous and jumbled aid system of device.The operating temperature for improving PEMFC not only can improve radiating efficiency to reduce the complexity of system,
It is additionally, since being lifted for catalytic efficiency so that the application of non-precious metal catalyst is possibly realized, and then to be expected to significantly drop
The cost of low fuel battery.Therefore, the successful exploitation of the high proton-conductive films of proton conductivity under cheap, high temperature low humidity
It is the key of the PEMFC of hot operation.
Being will be cheap for sulfonated polyether-ether-ketone (Sulfonated poly (ether ether ketone), sPEEK)
A kind of sulfonated prepared polymer dielectric of PEEK, because which has higher proton in certain humidity
Conductivity and in a fuel cell have preferable application prospect.In order to improve its proton conduction under high temperature low-moisture conditions
Rate, it is a kind of effective means to be doped modification using ionic liquid class compound to which.
Although existing proton-conductive films are with higher proton conduction property, but still existing defects.Firstly, since ionic liquid
The proton conductivity of body is relatively low at room temperature, directly mixes proton-conductive films prepared by sPEEK in room temperature using ionic liquid
Under be difficult to ensure battery startup optimization；Secondly as the strong water-soluble of ionic liquid, is directly mixed using ionic liquid
The ionic liquid in proton-conductive films prepared by sPEEK is easily lost with the current that electrode reaction is generated, and causes film properties to decline.
Therefore, research and development one kind can be efficiently applied to prepare Proton Exchange Membrane Fuel Cells, high temperature proton of good performance biography
Guided membrane material, is those skilled in the art's technical problem urgently to be resolved hurrily.
Content of the invention
In view of this, the invention provides a kind of crosslinked polyethers ether ketone high temperature proton-conductive films and preparation method thereof.The biography
Guided membrane has higher proton conductivity, and stable performance, it is adaptable to prepare the PEMC of different temperatures scope.
The concrete technical scheme of the present invention is as follows：
The invention provides a kind of cross-linked polyether-ether-ketone high temperature proton-conductive films, comprising：The nothing of Ionic Liquid Modified
Machine oxide nano particles and sulfonated polyether-ether-ketone.
Preferably, the mass ratio of the inorganic oxide nanoparticles of the Ionic Liquid Modified and the sulfonated polyether-ether-ketone
For 1:20～1:1.
Preferably, the inorganic oxide nanoparticles of the Ionic Liquid Modified be through ionic liquid silicon dioxide, two
Titanium oxide or zirconium dioxide；The particle diameter of the silicon dioxide, Titanium Dioxide and zirconium dioxide is 5～100nm.
Preferably, the ionic liquid is the alkyl-substituted heterocyclic nitrogen compounds of N-；The heterocyclic nitrogen compound bag
Include imidazoles, triazole or pyridine.
Preferably, the sulfonation degree of the sulfonated polyether-ether-ketone is 40%～90%.
Preferably, the sulfonated polyether-ether-ketone is passed through with the inorganic oxide nanoparticles of the ionic liquid doping vario-property
Interionic electrostatic attraction cross-linked polymeric.
Present invention also offers a kind of preparation method of crosslinked polyethers ether ketone high temperature proton-conductive films, including：
A) will be molten to alkyl-substituted for N- heterocyclic nitrogen compound, the inorganic oxide nanoparticles of modified by chloropropyl by and dispersion
Agent mixes, and is heated to reflux, and is centrifuged, and adds and is stirred in alcoholic solution, be centrifuged, collect precipitation, obtain the ionic liquid after drying
The inorganic oxide nanoparticles of body modification；
B) inorganic oxide nanoparticles of the Ionic Liquid Modified, the sulfonated polyether-ether-ketone and dispersion solvent are mixed
Close, ultrasound obtains mixed dispersion liquid；
C) mixed dispersion liquid is carried out heat treatment, obtains the crosslinked polyethers ether ketone high temperature proton-conductive films.
Preferably, described in step a), alcoholic solution includes：Tetrafluoroboric acid ethanol solution, trifluoromethane sulfonic acid ethanol solution or
Hexafluorophosphoric acid ethanol solution；
The alkyl-substituted heterocyclic nitrogen compound of the N- is the alkyl-substituted imidazoles of N-, triazole or pyridine.
Preferably, the time being heated to reflux described in step a) is 12h；The stirring is that 8h is stirred at room temperature.
Preferably, described in step c), heat treatment includes：At 80-120 DEG C, 10h is first bakeed, then dried at 140-160 DEG C
Roasting 10h；The time of the ultrasound is 30min.
Preferably, dispersion solvent described in step b) is ethylene glycol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, N- methyl
Ketopyrrolidine, N,N-dimethylformamide or dimethyl sulfoxide.
Preferably, the thickness of the described cross-linked polyether-ether-ketone high temperature proton-conductive films that the preparation method is prepared
For 15～115 μm.
The invention discloses a kind of crosslinked polyethers ether ketone high temperature proton-conductive films and preparation method thereof, provided by the present invention
Conductive membranes can rely on water under normal temperature condition as transmitting medium, conduct as proton by ionic liquid under the high temperature conditions
Medium, can adapt to different temperature ranges, stable performance, can be widely applied to prepare the proton for being applied to different temperatures scope
Exchange film fuel battery (PEMC)；As ionic liquid has been fixed on inorganic oxide nanoparticles surface, ion can be avoided
The hydraulic performance decline that the loss of liquid is caused such that it is able to keep stable performance.High polymer main chain is fixed to by ionic liquid
On preparation method compare, preparation method synthesis technique disclosed in this invention is relatively easy, and the conductive membranes for preparing are in height
There is under the conditions of temperature higher conductivity, stable performance.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Inventive embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, can be with basis
The accompanying drawing of offer obtains other accompanying drawings.
Transmission electron microscopes of the Fig. 1 for nano SiO 2 particle in the nano SiO 2 particle dispersion soln of modified by chloropropyl by
Photo；
Fig. 2 is the infrared spectrogram of the inorganic silicon dioxide nano granule of the Ionic Liquid Modified prepared in embodiment 1；
Fig. 3 is the stereoscan photograph of the crosslinked polyethers ether ketone high temperature proton-conductive films obtained in embodiment 1.
Specific embodiment
The invention discloses a kind of crosslinked polyethers ether ketone high temperature proton-conductive films and preparation method thereof, provided by the present invention
Conductive membranes have the advantages that high proton conducting power, stable performance, are applied to different temperatures scope, can be widely applied to prepare and fit
Proton Exchange Membrane Fuel Cells (PEMC) for different temperatures scope.Crosslinked polyethers ether ketone high temperature proton provided by the present invention
Conductive membranes be by nitrogen heterocycles Ionic Liquid Modified and sulfonated polyether-ether-ketone by electrostatic attraction be crosslinked prepared by form,
By modification of the ionic liquid to inorganic nanometer oxide nano-particle, realize ionic liquid is anchored at matter also while crosslinking
In sub- conductive membranes, it is to avoid the loss of ionic liquid, its preparation flow are as follows：
A kind of crosslinked polyethers ether ketone high temperature proton-conductive films provided by the present invention are sulfonated polyether-ether-ketone and inorganic oxide
A kind of quality of the thing nano-particle by material, inorganic oxide nanoparticles and sulfonated polyether-ether-ketone obtained from cross-linked polymeric
Than for 1:20～1:1, the sulfonation degree of sulfonated polyether-ether-ketone is 40%～90%.The thickness of the conductive membranes be 68～115 μm or
15～100 μm.
Inorganic oxide nanoparticles of the inorganic oxide nanoparticles in the conductive membranes for ionic liquid doping vario-property,
The ionic liquid is preferably the alkyl-substituted heterocyclic nitrogen compounds of N-, more preferably N- Methylimidazole .s；Wherein, the azepine
Cyclics also include triazole or pyridine.The inorganic oxide is preferably silicon dioxide, Titanium Dioxide or zirconium dioxide,
Particle diameter is preferably 5～100nm；The inorganic oxide is more preferably dioxy of the particle diameter for the silicon dioxide or 5-100nm of 30nm
Change titanium.
Present invention also offers the preparation method of the crosslinked polyethers ether ketone high temperature proton-conductive films, comprises the following steps：
(1) alkyl-substituted for N- heterocyclic nitrogen compound is added the inorganic nanometer oxide granule dispersion of chlorine alkyl modified
In liquid, certain time is heated to reflux, centrifugation post-drying obtains the inorganic oxygen of the Ionic Liquid Modified that anion is chloride ion
Compound nano-particle；
(2) by the anion prepared in step (1) for chloride ion Ionic Liquid Modified inorganic oxide nanometer
Granule is distributed in alcoholic solution carries out ion exchange, and centrifugation post-drying obtains the inorganic oxide of the Ionic Liquid Modified
Thing nano-particle；
(3) preparation-obtained for step (2) inorganic oxide nanoparticles dispersion liquid is added to sulfonated polyether-ether-ketone molten
In liquid, ultrasonic disperse obtains the inorganic oxide nanoparticles of Ionic Liquid Modified and the mixed dispersion liquid of sulfonated polyether-ether-ketone；
(4) mixed dispersion liquid is poured in politef culture dish, baking 10 hours at 100 DEG C, then
Bake and bank up with earth 4 hours in 150 DEG C of vacuum drying ovens again, the inorganic nanometer oxide and sulfonated polyether-ether-ketone for obtaining Ionic Liquid Modified is combined
Proton-conductive films, i.e. crosslinked polyethers ether ketone high temperature proton-conductive films.
Because anion is poor for the conductive performance of the inorganic oxide nanoparticles of the Ionic Liquid Modified of chloride ion, because
This is in step (2) by carrying out ion exchange in alcoholic solution.Wherein, the alcoholic solution preferably Tetrafluoroboric acid ethanol is molten
Liquid, trifluoromethane sulfonic acid ethanol solution or hexafluorophosphoric acid ethanol solution.
Crosslinked polyethers ether ketone high temperature proton-conductive films provided by the present invention, can rely on water as conduction under normal temperature condition
Medium, under the high temperature conditions by ionic liquid as proton conductive medium such that it is able to suitable for different temperatures scope；Due to
Ionic liquid has been fixed on inorganic oxide nanoparticles surface, the hydraulic performance decline that the loss of ionic liquid can be avoided to cause,
So as to keep stable performance；Additionally, preparation method ionic liquid being fixed on high polymer main chain is compared, the present invention
There is provided to prepare synthesis technique relatively easy.
Technical scheme is clearly and completely described below in conjunction with the specific embodiment of the invention, it is clear that
Described embodiment is a part of embodiment of the invention, rather than whole embodiments.It should be pointed out that for this technology neck
For the those of ordinary skill in domain, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these
Improvements and modifications also should be regarded as protection scope of the present invention.
Reagent employed in following examples is commercially available.
Embodiment 1
1st, the inorganic oxide nanoparticles of Ionic Liquid Modified are prepared
Using 50mL ethanol as dispersion solvent, 0.5g particle diameters are added for the silicon dioxide of the chloropropyl doping vario-property of 30nm
Grain, ultrasound, obtains the silica dioxide granule dispersion soln of modified by chloropropyl by.Silica nanometers of the Fig. 1 for modified by chloropropyl by
The transmission electron microscope photo of nano SiO 2 particle in grain dispersion soln, as shown in Fig. 1 results, the dioxy of chloropropyl doping vario-property
The particle diameter of silicon carbide particle is in 30nm or so, and is evenly distributed.
Carry out being heated to reflux 12h by the dispersion soln, centrifugation simultaneously washes away unreacted N- methyl miaow with dehydrated alcohol
Azoles, obtains the nano SiO 2 particle of the N- Methylimidazole. propyl group Ionic Liquid Modifieds that anion is chloride ion.Then will be upper
The nano SiO 2 particle for stating Ionic Liquid Modified is distributed to the Tetrafluoroboric acid ethanol solution of 0.1mol/L, and 8h is stirred at room temperature,
Centrifugation, obtains the silica nanometer of the N- Methylimidazole. propyl group Ionic Liquid Modifieds that anion is tetrafluoroborate
Grain.Fig. 2 is the nano SiO 2 particle infrared spectrogram of the above-mentioned Ionic Liquid Modified for preparing, in the infrared spectrogram
In 1774cm-1And 1593cm-1Place occurs in that the characteristic absorption peak of two imidazole rings, it was confirmed that the successful synthesis of sample.
2nd, the inorganic oxide nanoparticles of Ionic Liquid Modified and the mixed dispersion liquid of sulfonated polyether-ether-ketone are prepared
Using 20mL ethylene glycol as dispersion solvent, the nano SiO 2 particle of the Ionic Liquid Modified of 0.15g is added
In dispersion solvent, it is then added in the sulfonated polyether-ether-ketone ethylene glycol solution that 30mL sulfonation degree containing 0.45g is 67%, ultrasound point
Scattered 30min, obtains the nano SiO 2 particle of Ionic Liquid Modified and the mixed dispersion liquid of sulfonated polyether-ether-ketone.In the dispersion
In solution, the nano SiO 2 particle of Ionic Liquid Modified is dispersed and does not find agglomeration.
3rd, crosslinked polyethers ether ketone high temperature proton-conductive films are prepared
Prepared mixed dispersion liquid in step 2 is poured in politef culture dish, at 100 DEG C, bakees 10h,
Then carry out baking and banking up with earth 4h in 150 DEG C of vacuum drying ovens again, obtain the inorganic nanometer oxide and sulfonated polyether ether of Ionic Liquid Modified
The proton-conductive films that ketone is composited, the conductive membranes are light brown, thick 92 ± 8 μm.Wherein, Fig. 3 is high for the crosslinked polyethers ether ketone
The stereoscan photograph of warm proton-conductive films.
4th, crosslinked polyethers ether ketone high temperature proton-conductive films proton conductivity test
In humidity 100%, temperature detects that crosslinked polyethers ether ketone high temperature proton is passed under conditions of being respectively 25,40,60,80 DEG C
Guided membrane proton conductivity.Crosslinked polyethers ether ketone high temperature matter is detected under the conditions of dry state, temperature are respectively 100,120,140,160 DEG C
Sub- conductive membranes proton conductivity.As shown in table 1, under 100～160 DEG C of dry state hot conditionss, proton conductivity is not or not testing result
It is less than 0.0065S cm-1, under 25～100 DEG C of humidified conditions, proton conductivity is not less than 0.045S cm-1.
The proton conductivity of the sample prepared by 1 embodiment 1 of table.
Embodiment 2
Same as Example 1, difference is：Replace two with the titania nanoparticles that particle diameter is 5nm in step 1
Silica nano particle, trifluoromethane sulfonic acid replace Tetrafluoroboric acid, and the solvent in step 2 is N-Methyl pyrrolidone.Remaining step
Rapid and consumption is same as Example 1.The membrane sample for preparing is light brown, and thickness is 89 ± 10 μm.The proton that is tested is passed
The proton conductivity of guided membrane is shown in Table 2, and under 100～160 DEG C of dry conditions, proton conductivity is not less than 0.0065S cm-1, 25
Under～100 DEG C of humidified conditions, proton conductivity is not less than 0.045S cm-1.
The proton conductivity of the sample prepared by 2 embodiment 2 of table.
Embodiment 3
Same as Example 1, difference is：Replaced with the titania nanoparticles that particle diameter is 100nm in step 1
Nano SiO 2 particle, trifluoromethane sulfonic acid replace Tetrafluoroboric acid, the solvent in step 2 be N-Methyl pyrrolidone, sulfonation
The sulfonation degree of polyether-ether-ketone is 90%, and the quality of the titania nanoparticles of Ionic Liquid Modified is 0.0225g；Remaining step
Same as Example 1 with consumption.Preparation-obtained membrane sample is light brown, and thickness is 76 ± 8 μm.The proton conduction that is tested
The proton conductivity of film is shown in Table 3.Under 100～160 DEG C of dry conditions, proton conductivity is not less than 0.0065S cm-1, 25～
Under 100 DEG C of humidified conditions, proton conductivity is not less than 0.045S cm-1.
The proton conductivity of the sample prepared by 3 embodiment 3 of table.
Embodiment 4
Same as Example 1, difference is：Replace two with the titania nanoparticles that particle diameter is 5nm in step 1
Silica nano particle, trifluoromethane sulfonic acid replace Tetrafluoroboric acid, the solvent in step 2 be N-Methyl pyrrolidone, sulfonation gather
The sulfonation degree of ether ether ketone is 40%, and the quality of the titania nanoparticles of Ionic Liquid Modified is 0.45g, remaining step and use
Amount is same as Example 2.Prepared membrane sample is light brown, and thickness is 100 ± 15 μm.The matter of the proton-conductive films that is tested
Sub- conductivity is shown in Table 4.Under 100～160 DEG C of dry conditions, proton conductivity is not less than 0.0065S cm-1, at 25～100 DEG C
Under humidified condition, proton conductivity is not less than 0.041S cm-1.
The proton conductivity of the sample prepared by 4 embodiment 4 of table
Embodiment 5
Same as Example 1, difference is：1- methyl isophthalic acids, 2,4 triazoles is used to replace N- Methylimidazole .s in step 1, its
Remaining step and consumption are same as Example 1.Prepared membrane sample is light brown, and thickness is 90 ± 6 μm.The proton that is tested is passed
The proton conductivity of guided membrane is shown in Table 5, and under 100～160 DEG C of dry state hot conditionss, proton conductivity is not less than 0.0065S cm-
1, under 25～100 DEG C of humidified conditions, proton conductivity is not less than 0.037S cm-1.
The proton conductivity of the sample prepared by 5 embodiment 5 of table.
Claims (12)
1. a kind of cross-linked polyether-ether-ketone high temperature proton-conductive films, comprising：The inorganic oxide nanometer of Ionic Liquid Modified
Grain and sulfonated polyether-ether-ketone.
2. cross-linked polyether-ether-ketone high temperature proton-conductive films according to claim 1, it is characterised in that the ionic liquid
The mass ratio of the inorganic oxide nanoparticles of body modification and the sulfonated polyether-ether-ketone is 1:20～1:1.
3. cross-linked polyether-ether-ketone high temperature proton-conductive films according to claim 1, it is characterised in that the ionic liquid
The inorganic oxide nanoparticles of body modification are through the silicon dioxide of ionic liquid chemical graft, Titanium Dioxide or zirconium dioxide；
The particle diameter of the silicon dioxide, Titanium Dioxide and zirconium dioxide is 5～100nm.
4. cross-linked polyether-ether-ketone high temperature proton-conductive films according to claim 1, it is characterised in that the ionic liquid
Body is the alkyl-substituted heterocyclic nitrogen compounds of N-；
The heterocyclic nitrogen compound includes imidazoles, triazole or pyridine.
5. cross-linked polyether-ether-ketone high temperature proton-conductive films according to claim 1, it is characterised in that the sulfonation gathers
The sulfonation degree of ether ether ketone is 40%～90%.
6. cross-linked polyether-ether-ketone high temperature proton-conductive films according to claim 1, it is characterised in that the sulfonation gathers
Ether ether ketone passes through interionic electrostatic attraction cross-linked polymeric with the inorganic oxide nanoparticles of the ionic liquid doping vario-property.
7. the preparation method of the crosslinked polyethers ether ketone high temperature proton-conductive films as described in claim 1-6, including：
A) alkyl-substituted for N- heterocyclic nitrogen compound, the inorganic oxide nanoparticles of modified by chloropropyl by and dispersion solvent are mixed
Close, be heated to reflux, be centrifuged, add after drying and be stirred in alcoholic solution, be centrifuged, collect precipitation, obtain the ionic liquid and repair
The inorganic oxide nanoparticles of decorations；
B) inorganic oxide nanoparticles of the Ionic Liquid Modified, the sulfonated polyether-ether-ketone and dispersion solvent are mixed,
Ultrasound, obtains mixed dispersion liquid；
C) mixed dispersion liquid is carried out heat treatment, obtains the crosslinked polyethers ether ketone high temperature proton-conductive films.
8. preparation method according to claim 7, it is characterised in that alcoholic solution includes described in step a)：Tetrafluoroboric acid
Ethanol solution, trifluoromethane sulfonic acid ethanol solution or hexafluorophosphoric acid ethanol solution；
The alkyl-substituted heterocyclic nitrogen compound of the N- is the alkyl-substituted imidazoles of N-, triazole or pyridine.
9. preparation method according to claim 7, it is characterised in that the time being heated to reflux described in step a) is 12h；
The stirring is that 8h is stirred at room temperature.
10. preparation method according to claim 7, it is characterised in that heat treatment includes described in step c)：First in 80-
10h is bakeed at 120 DEG C, then bakees 10h at 140-160 DEG C；
The time of the ultrasound is 30min.
11. preparation methoies according to claim 7, it is characterised in that dispersion solvent described in step b) is ethylene glycol, second
Alcohol, normal propyl alcohol, isopropanol, n-butyl alcohol, N-Methyl pyrrolidone, N,N-dimethylformamide or dimethyl sulfoxide.
12. preparation methoies according to claim 7, it is characterised in that the crosslinking that the preparation method is prepared
The thickness of sulfonated polyether-ether-ketone high temperature proton-conductive films is 15～115 μm.
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Cited By (4)
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| CN107808969A (en) * | 2017-09-27 | 2018-03-16 | 广西大学 | A kind of preparation method of high temperature proton exchange film |
| CN108110291A (en) * | 2017-12-28 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel cell refractory ceramics matrix proton exchange and preparation method thereof |
| CN111333892A (en) * | 2020-03-19 | 2020-06-26 | 辽宁科京新材料科技有限公司 | Preparation method of organic/inorganic amphoteric ion conduction composite membrane |
| CN111342096A (en) * | 2020-03-09 | 2020-06-26 | 长春工业大学 | Pyridine cross-linked anion exchange membrane for fuel cell and preparation method thereof |
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| CN101604757A (en) * | 2009-04-27 | 2009-12-16 | 武汉理工新能源有限公司 | Used for high-temperature fuel cell proton exchange membrane and preparation method thereof in a kind of |
| CN101908632A (en) * | 2010-07-15 | 2010-12-08 | 上海大学 | Ternary doping modified SPEEK proton exchange membrane and preparation method |
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| CN101604757A (en) * | 2009-04-27 | 2009-12-16 | 武汉理工新能源有限公司 | Used for high-temperature fuel cell proton exchange membrane and preparation method thereof in a kind of |
| CN101908632A (en) * | 2010-07-15 | 2010-12-08 | 上海大学 | Ternary doping modified SPEEK proton exchange membrane and preparation method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107808969A (en) * | 2017-09-27 | 2018-03-16 | 广西大学 | A kind of preparation method of high temperature proton exchange film |
| CN107808969B (en) * | 2017-09-27 | 2020-11-20 | 广西大学 | Preparation method of high-temperature proton exchange membrane |
| CN108110291A (en) * | 2017-12-28 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel cell refractory ceramics matrix proton exchange and preparation method thereof |
| CN111342096A (en) * | 2020-03-09 | 2020-06-26 | 长春工业大学 | Pyridine cross-linked anion exchange membrane for fuel cell and preparation method thereof |
| CN111342096B (en) * | 2020-03-09 | 2022-10-04 | 长春工业大学 | Pyridine cross-linked anion exchange membrane for fuel cell and preparation method thereof |
| CN111333892A (en) * | 2020-03-19 | 2020-06-26 | 辽宁科京新材料科技有限公司 | Preparation method of organic/inorganic amphoteric ion conduction composite membrane |
| CN111333892B (en) * | 2020-03-19 | 2022-09-13 | 辽宁科京新材料有限公司 | Preparation method of organic/inorganic amphoteric ion conduction composite membrane |
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