CN103897336A - Sulfonated polyether-ether-ketone/phosphorylated mesoporous silica hybrid membrane preparation and application - Google Patents

Sulfonated polyether-ether-ketone/phosphorylated mesoporous silica hybrid membrane preparation and application Download PDF

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CN103897336A
CN103897336A CN201410093432.1A CN201410093432A CN103897336A CN 103897336 A CN103897336 A CN 103897336A CN 201410093432 A CN201410093432 A CN 201410093432A CN 103897336 A CN103897336 A CN 103897336A
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ether
ketone
phosphorylation
silicon oxide
film
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姜忠义
赵宇宁
吴洪
杨昊
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Tianjin University
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Tianjin University
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to sulfonated polyether-ether-ketone/phosphorylated mesoporous silica hybrid membrane preparation and application, and relates to a phosphorylated mesoporous silica submicron spherical particle, and a preparation method and application of a phosphorylated hybrid membrane. The preparation process comprises the following steps: synthesizing the mesoporous silica submicron spherical particles, phosphorylating epoxy group silane coupling agent modified particles and phosphorus oxychloride to obtain the phosphorylated mesoporous silica; filling particles into a sulfonated polyether-ether-ketone membrane matrix, thermally treating to prepare the phosphorylated hybrid membrane. The preparation process condition of the phosphorylated silica particle is simple and efficient, the prepared hybrid membrane is uniform, good in organic-inorganic compatibility, and can be used for direct methanol fuel cell system. The highest membrane proton conduction rate can achieve 0.2407Scm-1 (the temperature is 60 DEG.C, the relative humidity is 100%, and the filling amount of the phosphorylated mesoporous silica particle is 5wt.%).

Description

The preparation of sulfonated polyether-ether-ketone/phosphorylation mesoporous silicon oxide hybridized film and application
Technical field
The present invention relates to a kind of sulfonated polyether-ether-ketone/phosphorylation mesoporous silicon oxide submicron spherical particle hybridized film and its preparation method and application, belong to hybrid inorganic-organic proton exchange membrane used for direct methanol fuel cell field, especially relate to the preparation method and application of phosphorylation mesoporous silicon oxide submicron spherical particle.
Background technology
There is respectively electrochemical oxidation, reduction reaction by fuel and oxygenant in fuel cell, and chemical energy is converted into electric energy by direct generation current.The advantages such as compared with the traditional energy such as oil engine, battery, it is high that fuel cell has effciency of energy transfer, and the pollutent that discharges without combustion of fossil fuel, fuel type are many.Wherein, direct methanol fuel cell (direct methanol fuel cell, DMFC) is the hydrogen generation oxidizing reaction that adopts platinum ruthenium catalyst catalytic fluid methyl alcohol, methyl alcohol specific energy density is high, and source is abundant, and electrochemical activity is high, DMFC normal temperature starts rapidly, with low cost, has a extensive future.Proton exchange membrane (proton exchange membrane, PEM) is one of DMFC most critical parts, is the key component that improves fuel cell energy transformation efficiency.
After within 1992, developing, regular Metaporous silicon dioxide material (mesoporous size range is: 2-50 nm) because it has that specific surface area is high, duct, structural stability advantages of higher controlled at nanoscale, skeleton construction obtain broad research.Its mesopore orbit can be fixed water molecules by capillary action, simultaneously can load proton transfer group, at the inner proton transfer passage that forms of mesopore orbit, improve film proton conductivity.Phosphate radical is as proton transfer site, have proton acceptor, protophobe characteristic concurrently, the proton density that specific inductivity is high, can form more sufficient hydrogen bond network system and Geng Gao, compared with the proton transfer such as sulfonate radical, amino group, the water of phosphate radical, in conjunction with can higher, average zero-point energy low, can improve film water retention capacity and reduce proton jump energy barrier.The thermostability of phosphate radical is also better than sulfonate radical in addition.Proton exchange membrane based on phosphate radical becomes study hotspot gradually.Phosphate radical is fixed on to mesoporous material surface and duct inwall, can in film, introduces higher water retention capacity and novel proton transfer passage, thus the proton conduction property of reinforced film.Up to the present, sulfonated polyether-ether-ketone/phosphorylation mesoporous silicon oxide hybridized film has no bibliographical information for the proton exchange membrane of direct methanol fuel cell.
Summary of the invention
The object of the present invention is to provide a kind of hybrid inorganic-organic proton exchange membrane used for direct methanol fuel cell, it is prepared by the following method: first prepare mesoporous silicon oxide submicron spherical particle (MPS), then by epoxy silane coupling to its modifying surface, introduce epoxy group(ing), re-using phosphorus oxychloride carries out phosphorylation and prepares phosphorylation mesoporous silicon oxide submicron spherical particle (PMPS), finally itself and sulfonated polyether-ether-ketone (SPEEK) are synthesized to sulfonated polyether-ether-ketone/phosphorylation mesoporous silicon oxide submicron spherical particle (SPEEK/PMPS) hybridized film by casting method.
Phosphorylation mesoporous silicon oxide submicron spherical particle provided by the invention is prepared as follows.
1) preparation of mesoporous silicon oxide submicron spherical particle (MPS):
Adopt classical MCM-41 molecular sieve preparation method to prepare the mesoporous silicon oxide submicron spherical particle with template: under vigorous stirring by CTAB(cetyl trimethylammonium bromide, hexadecyl trimethyl ammonium bromide, CTAB), 2 M aqueous sodium hydroxide solutions are in 80 oc is dissolved in deionized water, the wherein CTAB 0.083 wt.%-0.25 wt.% of ionized water massfraction that accounts for, account for 0.73 vol.% of ionized water volume fraction of sodium hydroxide.After dissolving completes, to the silane precursor (tetraethoxy, tetraethyl orthosilicate, TEOS) that adds 1.04 vol.% in solution, keep afterwards 80 oc stirs 2-5 hour.Centrifugation obtains solid phase prod, and after deionized water wash three times, product is in room temperature vacuum-drying to constant weight, and products obtained therefrom is with template mesoporous silicon oxide submicron spherical particle.
Removal with template mesoporous silicon oxide submicron spherical granular formwork: above-mentioned synthetic particle is scattered in methanolic hydrochloric acid solution (solution quality is granular mass 60 times, wherein hydrochloric acid to account for the volume content of methyl alcohol be 5.625 vol.%), refluxes 48 hours.Centrifugation obtains solid phase prod, and after deionized water wash three times, product is in room temperature vacuum-drying to constant weight, and products obtained therefrom is pure mesoporous silicon oxide submicron spherical particle, is designated as MPS.
2) preparation of phosphorylation mesoporous silicon oxide submicron spherical particle (PMPS):
MPS particle is scattered in excessive dry toluene, the epoxy silane coupling (3-glycidyl oxygen propyl trimethoxy silicane, 3-glycidyloxypropyltrimethoxysilane, GPTMS) of quality such as add, back flow reaction 24 hours, carries out epoxy group(ing) modification to MPS.Centrifuge washing, is scattered in gained epoxy group(ing) modified particles in excessive phosphorus oxychloride, refluxes and particle is carried out to phosphorylation in 24 hours.Centrifuge washing, obtains the mesoporous silicon oxide submicron spherical particle PMPS of phosphorylation.
3) preparation of sulfonated polyether-ether-ketone:
Dry polyether-ether-ketone particle is dissolved in (polyether-ether-ketone is 28 wt./vol.% with respect to vitriol oil mass/volume mark) in the vitriol oil, vigorous stirring under room temperature until polyether-ether-ketone particle dissolve completely, at room temperature continue subsequently violent stirring and carry out sulfonation reaction, spend the night (8-14 hour) obtains the thick solution of reddish-brown.Gained liquid pouring, in a large amount of deionized waters, obtains rapidly white precipitate, then soaks with a large amount of deionized waters, flushing gained precipitation, until washings is neutral, final product was air drying 24 hours, at room temperature vacuum-drying 24 hours, can obtain dry sulfonated polyether-ether-ketone.
4) preparation of hybridized film:
Be scattered in DMF (DMF) ultrasonic a certain amount of PMPS, disperse to spend the night.Account for the SPEEK that film-casting liquid total mass/volume fraction is 10 wt./vol.%, stirring at room temperature 24 hours to adding in dispersion liquid.By after film-casting liquid deaeration on sheet glass curtain coating, first 60 odried overnight film forming under C, then 100 o anneal 4 hours under C.The aqueous sulfuric acid acidifying of gained mould material, then washing is to neutral, the dry hybridized film that obtains.The thickness of gained film is in 80 μ m left and right.
The invention has the advantages that: by realizing particle phosphorus acidifying in the method for mesoporous silicon oxide submicron spherical particle outside surface and duct inwall introducing epoxy group(ing), process is gentle simple, has overcome silica sphere silicon hydroxyl inertia and has been difficult for the shortcoming of reacting.Phosphate radical is successfully fixed on silicon-dioxide, in film, efficiently introduces phosphate radical as proton transfer group.After being packed into SPEEK film, can obtain uniform phosphorylation hybrid organic-inorganic film.The mesoporous silicon oxide submicron spherical particle of phosphorylation can be used as proton conductor, and capillary action adsorbed water molecule can be passed through in inside, mesoporous particles duct simultaneously, forms proton transfer passage, has improved hybridized film proton conduction property.The prepared phosphorylation hybridized film of the inventive method SPEEK/PMPS, during for direct methanol fuel cell, 60 ounder the condition of C, relative humidity 100%, conductivity is up to 0.2407 S cm -1, be in the methanol aqueous solution of 2 M in concentration, room temperature 25 ounder C condition, methanol permeability is minimum reaches 2.29 × 10 -7cm 2s -1.
Accompanying drawing explanation
Film proton conductivity comparison diagram in temperature-rise period under 100% RH test condition in Fig. 1 embodiment and comparative example.
The methanol permeability comparison diagram of film under room temperature, 2 mol/L methanol aqueous solution test conditions in Fig. 2 embodiment and comparative example.
The transmission electron microscope picture (HRTEM-JEM-2100F type HRTEM, JEOL company) of made phosphorylation mesoporous silicon oxide submicron spherical particle in Fig. 3 embodiment 2.
The transmission electron microscope picture of made mesoporous silicon oxide submicron spherical particle (HRTEM-JEM-2100F type HRTEM, JEOL company) in Fig. 4 embodiment 1.
The section Electronic Speculum figure of made film SPEEK/PMPS-5 in Fig. 5 embodiment 4 (Nanosem 430 type FESEM, FEI Co.).
The section Electronic Speculum figure of made comparative film SPEEK in Fig. 6 comparative example 1 (Nanosem 430 type FESEM, FEI Co.).
The section Electronic Speculum figure of made comparative film SPEEK/MPS-5 in Fig. 7 comparative example 2 (Nanosem 430 type FESEM, FEI Co.).
Embodiment
The preparation of embodiment 1 MPS
Under vigorous stirring by CTAB(0.4 g), 2 mol/L aqueous sodium hydroxide solutions (3.5 mL) are dissolved in 480 mL deionized waters (80 oc).After dissolving completes, to the TEOS that adds 5 mL in solution, keep afterwards 80 oc stirs 3 hours.Centrifugation obtains solid phase prod, and after deionized water wash three times, product is in room temperature vacuum-drying to constant weight.
(1.2 g) are scattered in (9 mL concentrated hydrochloric acids are dissolved in 160 mL anhydrous methanols and form) in methanolic hydrochloric acid solution, reflux 48 hours to get above-mentioned synthetic particle.Centrifugation obtains solid phase prod, and after deionized water wash three times, product is in room temperature vacuum-drying to constant weight.Products obtained therefrom is mesoporous silicon oxide submicron spherical particle, i.e. MPS.
The preparation of embodiment 2 PMPS
As above the synthetic MPS of method is scattered in dry toluene (60 times that quality is MPS), the GPTMS of quality such as adds, back flow reaction 24 hours.Centrifugal and with ethanol, water washing three times, product, in room temperature vacuum-drying to constant weight, obtains epoxy group(ing) modification MPS.Above-mentioned epoxy group(ing) modification MPS particle is scattered in to (phosphorus oxychloride quality is 60 times of granular mass) in excessive phosphorus oxychloride, refluxes 24 hours.Centrifugal and with ethanol, water washing three times, obtain phosphorylation mesoporous silicon oxide submicron spherical particle PMPS after dry.
The preparation of embodiment 3 SPEEK
28 grams of dry polyether-ether-ketone particles are dissolved in the 100 mL vitriol oils, and vigorous stirring under room temperature, until polyether-ether-ketone particle dissolves completely, at room temperature continues subsequently violent stirring and carries out sulfonation reaction and within 14 hours, obtain the thick solution of reddish-brown.Gained liquid pouring, in a large amount of deionized waters, obtains rapidly white precipitate, then soaks with a large amount of deionized waters, flushing gained precipitation, until washings is neutral, finally by product air drying 24 hours, room temperature vacuum-drying 24 hours, obtains dry sulfonated polyether-ether-ketone.
The preparation of embodiment 4 SPEEK/PMPS hybridized film
Take a certain amount of ultrasonic being scattered in 6 mL DMF of PMPS particle of preparing as embodiment 2.To the SPEEK that dissolves 0.6 g under magnetic agitation condition in dispersion liquid, stirring at room temperature 24 hours.After deaeration by film-casting liquid curtain coating on sheet glass, first 60 odry 12 hours film forming under C, then 100 ounder C, anneal 4 hours, obtains film.Acidifying 24 hours in the aqueous sulfuric acid of 2 M subsequently, washes away residual sulfuric acid with deionized water, until washings is neutral, finally 25 ounder C, vacuum-drying film is to constant weight.The numbering of prepared film is respectively SPEEK/PMPS-5, SPEEK/PMPS-10, SPEEK/PMPS-15, and wherein inorganic materials PMPS consumption is respectively 5 wt.%, 10 wt.%, 15 wt.% of sulfonated polyether-ether-ketone consumption.
The preparation of the pure SPEEK film of comparative example 1
The SPEEK of 0.6 gram is dissolved in the DMF of 6 mL to stirring at room temperature 24 hours.After deaeration by film-casting liquid curtain coating on sheet glass, first 60 odry 12 hours film forming under C, then 100 ounder C, anneal obtains film for 4 hours.Acidifying 24 hours in the aqueous sulfuric acid of 2 M subsequently, washes away residual sulfuric acid with deionized water, until washings is neutral, finally 25 ounder C, vacuum-drying film, to constant weight, does not contain organic and/or inorganic materials in gained SPEEK film.
The preparation of comparative example 2 SPEEK/MPS hybridized film
Take in a certain amount of ultrasonic DMF that is scattered in 6 mL of MPS particle preparing as embodiment 1.Dissolve to adding in dispersion liquid under the SPEEK magnetic agitation of 0.6 gram.After deaeration by film-casting liquid curtain coating on sheet glass, first 60 odry 12 hours film forming under C, then 100 ounder C, anneal obtains film for 4 hours.Acidifying 24 hours in the aqueous sulfuric acid of 2 M subsequently, washes away residual sulfuric acid with deionized water, until washings is neutral, finally 25 ounder C, vacuum-drying film is to constant weight.The numbering of prepared film is respectively SPEEK/MPS-5, SPEEK/MPS-10, SPEEK/MPS-15, and wherein inorganic materials MPS consumption is respectively 5 wt.%, 10 wt.%, 15 wt.% of sulfonated polyether-ether-ketone consumption.
Test condition
The mould material proton conductivity test condition making in embodiment and comparative example is: the humidity of controlling diaphragm material is 100% RH, by using electrochemical workstation (electrochemical workstation in room temperature temperature-rise period, PARSTAT 2273, Princeton) level of test membrane material is to proton conductivity.In test process, temperature is elevated to certain numerical value, reach the highest tolerable temperature of mould material under 100% RH, while exceeding this temperature, the destruction of mould material recurring structure, cannot measure proton conductivity, therefore the end temp of mould material proton conduction is the highest tolerable temperature under 100% RH again, has reflected the hydrothermal stability of mould material under test condition.The methanol permeability test condition of mould material is in 2 mol/L methanol solutions, under room temperature condition, test methyl alcohol sees through the spread coefficient of film, the i.e. methanol permeability of film.
As can be seen from Figure 1 prepare after SPEEK/PMPS hybridized film to inserting PMPS particle in SPEEK film, SPEEK/PMPS-5 under 100% RH test condition whole temperature range inner proton conductivity all higher than pure film.Contrast two kinds of hybridized film, SPEEK/PMPS hybridized film proton conductivity is all higher than the proton conductivity of SPEEK/MPS hybridized film under identical loading level.Illustrate that fill PMPS has introduced the novel proton transfer of phosphate radical site in film, simultaneously mesopore orbit inwall adsorbed water molecule, can form novel proton transfer passage, reinforced film proton conductivity.As can be seen from Figure 2, insert inorganic particle PMPS, MPS in SPEEK film after, hybridized film methanol permeability is all lower than pure film, and further declines along with loading level improves methanol permeability, and SPEEK/PMPS hybridized film resistance alcohol ability is the strongest, higher than SPEEK/MPS hybridized film.The effect that hinders methanol molecules material transfer has been played in the introducing that inorganic materials is described, has improved the alcohol-rejecting ability of mould material, and along with the increase of inorganic materials massfraction in film, and present the trend that methanol permeability is inhibited.With having stronger ionic linkage, interaction of hydrogen bond between the PMPS of acid group and membrane matrix, therefore its resistance alcohol ability is the highest.From Fig. 1, it can also be seen that under 100% RH proton conductivity test condition, mould material is the highest can tolerable temperature, and the accessible high proton conductivity of mould material.It is 55 that the pure film of SPEEK and SPEEK/MPS film can tolerate top temperature under 100% RH test condition oc, inserts the highest tolerable temperature of PMPS and can be promoted to 60 oc, this explanation PMPS has stronger stability structure, the structure of SPEEK/PMPS hybridized film has strengthened the hydrothermal stability of mould material, ionic linkage between PMPS and membrane matrix, interaction of hydrogen bond have strengthened the hydrothermal stability of film under 100% RH condition, have improved the adaptive faculty of film under test condition.
In sum, PMPS is introduced to the SPEEK/PMPS hybridized film obtaining after SPEEK membrane matrix and has the proton conductivity of enhancing, excellent hydrothermal stability, is applied to and in DMFC, has certain advantage, and its high proton conductivity can reach 0.2407 S cm -1(SPEEK/PMPS-5,60 oc, 100% RH), hydrothermal stability can reach 60 oc, and hinder preferably alcohol characteristic (2.29 × 10 -7cm 2s -1).

Claims (4)

1. sulfonated polyether-ether-ketone/phosphorylation mesoporous silicon oxide submicron spherical particle hybridized film, it is characterized in that take phosphorylation mesoporous silicon oxide submicron spherical particle as hybrid medium, sulfonated polyether-ether-ketone is membrane matrix, the 5 wt.%-15 wt.% that phosphorylation mesoporous silica particles content is sulfonated polyether-ether-ketone.
2. a preparation method for sulfonated polyether-ether-ketone/phosphorylation mesoporous silicon oxide submicron spherical particle hybridized film as claimed in claim 1, is characterized in that it comprises the following steps:
1) with concentrated acid sulfonation polyether-ether-ketone particle, obtain sulfonated polyether-ether-ketone polymer matrix membrane;
2) phosphorylation mesoporous silicon oxide submicron spherical particle is scattered in to N, in dinethylformamide, form dispersion liquid, then sulfonated polyether-ether-ketone is dissolved in dispersion liquid, fully stir and form film-casting liquid, after deaeration by film-casting liquid curtain coating on sheet glass, through intensification 60 oc drying treatment, high temperature 100 oc anneal, obtains phosphorylation hybridization film material.
3. a preparation method as claimed in claim 2, is characterized in that phosphorylation mesoporous silicon oxide submicron spherical particle prepared as follows:
1) take cetyl trimethylammonium bromide as template, prepare mesoporous silicon oxide submicron spherical particle, in methanolic hydrochloric acid solution, remove template, obtain mesoporous silicon oxide submicron spherical particle;
2) using epoxy silane coupling to step 1) mesoporous silica particles that makes carries out modification, make its outside surface epoxy group(ing), use afterwards phosphorus oxychloride to carry out phosphorylation to particle, make phosphorylation mesoporous silicon oxide submicron spherical particle.
4. sulfonated polyether-ether-ketone/phosphorylation mesoporous silicon oxide submicron spherical particle hybridized film as claimed in claim 1 application in direct methanol fuel cell.
CN201410093432.1A 2014-03-13 2014-03-13 Sulfonated polyether-ether-ketone/phosphorylated mesoporous silica hybrid membrane preparation and application Pending CN103897336A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104209023A (en) * 2014-08-27 2014-12-17 天津大学 Sulfonated poly(ether ether ketone)-sulfonated silicon dioxide microsphere hybrid membrane, as well as preparation and application of membrane
CN104212153A (en) * 2014-08-27 2014-12-17 天津大学 Sulfonated polyether ether ketone and carboxylated silicon dioxide microsphere hybrid membrane as well as preparation method and application of sulfonated polyether ether ketone and carboxylated silicon dioxide microsphere hybrid membrane
CN108075160A (en) * 2017-12-29 2018-05-25 成都新柯力化工科技有限公司 The glass base fuel battery proton exchange membrane and preparation method of a kind of high-temperature stable
CN108070098A (en) * 2017-12-19 2018-05-25 长春工业大学 Fuel cell inorganic particulate compoiste proton exchange film and preparation method thereof
CN109777037A (en) * 2019-02-18 2019-05-21 山东星火科学技术研究院 The preparation method of phosphorylation sulfonated polyether-ether-ketone and Nano particles of silicon dioxide composite membrane
CN114367202A (en) * 2022-01-12 2022-04-19 安徽大学 Preparation method of sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis

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CN103304979A (en) * 2013-07-26 2013-09-18 天津大学 Phosphorylation titanium dioxide hollow sphere-filled sulfonated polyether ether ketone film as well as preparation and application
CN103474680A (en) * 2013-08-09 2013-12-25 上海交通大学 Super absorbent proton exchange membrane and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304979A (en) * 2013-07-26 2013-09-18 天津大学 Phosphorylation titanium dioxide hollow sphere-filled sulfonated polyether ether ketone film as well as preparation and application
CN103474680A (en) * 2013-08-09 2013-12-25 上海交通大学 Super absorbent proton exchange membrane and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104209023A (en) * 2014-08-27 2014-12-17 天津大学 Sulfonated poly(ether ether ketone)-sulfonated silicon dioxide microsphere hybrid membrane, as well as preparation and application of membrane
CN104212153A (en) * 2014-08-27 2014-12-17 天津大学 Sulfonated polyether ether ketone and carboxylated silicon dioxide microsphere hybrid membrane as well as preparation method and application of sulfonated polyether ether ketone and carboxylated silicon dioxide microsphere hybrid membrane
CN108070098A (en) * 2017-12-19 2018-05-25 长春工业大学 Fuel cell inorganic particulate compoiste proton exchange film and preparation method thereof
CN108075160A (en) * 2017-12-29 2018-05-25 成都新柯力化工科技有限公司 The glass base fuel battery proton exchange membrane and preparation method of a kind of high-temperature stable
CN109777037A (en) * 2019-02-18 2019-05-21 山东星火科学技术研究院 The preparation method of phosphorylation sulfonated polyether-ether-ketone and Nano particles of silicon dioxide composite membrane
CN114367202A (en) * 2022-01-12 2022-04-19 安徽大学 Preparation method of sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis

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Application publication date: 20140702