CN105597568A - Chloromethylated polyether-ether-ketone/imidazole carbon nano tube hybrid membrane, preparation and application - Google Patents
Chloromethylated polyether-ether-ketone/imidazole carbon nano tube hybrid membrane, preparation and application Download PDFInfo
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- 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
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- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
The invention discloses a chloromethylated polyether-ether-ketone/imidazole carbon nano tube hybrid membrane with the thickness of 70-120 micrometers. The hybrid membrane is composed of chloromethylated polyether-ether-ketone and an imidazole modified carbon nano tube, wherein the mass ratio of the imidazole carbon nano tube to the chloromethylated polyether-ether-ketone is 0.05-0.2:1. A preparation method comprises the steps that chloromethylated octyl ether is prepared as a chloromethylated reagent; the polyether-ether-ketone reacts with the chloromethylated octyl ether to obtain the chloromethylated polyether-ether-ketone; the imidazole modified carbon nano tube is prepared; the imidazole modified carbon nano tube and the chloromethylated polyether-ether-ketone are mixed to obtain membrane casting liquid, and the hybrid membrane is prepared through flow casting. The preparation process of the hybrid membrane is easy to operate, environmentally friendly and convenient and fast to implement. The obtained chloromethylated polyether-ether-ketone/imidazole carbon nano tube hybrid membrane is applied to an ion exchange membrane fuel battery, and has the high hydroxyl ion conductivity and ideal swelling resistance.
Description
Technical field
The present invention relates to a kind of chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film and preparation and application, belong to ion and hand overChange membrane cell technical field.
Background technology
Since stepping into 21 century, growing along with world energy consumption amount, energy problem becomes increasingly conspicuous. Energy reserveThe problem such as environmental pollution, greenhouse effects that exhausted, traditional fossil energy is brought can not be ignored, development of new, efficient, greenThe energy is extremely urgent. Fuel cell be a kind of without burning directly the chemical energy being stored in fuel and oxidant is converted intoThe electrochemical apparatus of electric energy, because of its green, safety, the feature such as clean, efficient, is widely used in military affairs, communication, automobileWith fields such as Aero-Space, be described as the most promising novel energy of 21st century.
Amberplex, as the core component of fuel cell, plays a part to separate anode and cathode reactant, conducting ion. ReasonThe amberplex of thinking should have higher ionic conductance, higher fuel gas barrier properties, and enough mechanical strengths, goodGood heat, chemical stability, and cheap and easy to get. The amberplex of report is divided into two kinds, PEM (Proton at presentExchangemembrane, PEM) and hydroxide ion exchange membrane (Anionexchangemembrane, AEM), two kindsMembrane material differs from one another, and compared to PEM, and hydroxide ion exchange membrane has been broken away from noble metal catalysts such as platinumRely on, greatly reduce operating cost; In alkaline electrolyte, the activity of catalyst compared with under acid condition greatly promote, andAnd alkaline electrolyte has reduced the corrosion to fuel cell module. Therefore, in recent years, hydroxide ion exchange membrane is because it is onlySpecial advantage, causes that Chinese scholars pays close attention to more widely, but general ionic conductance, height lower than PEMThe problems such as the lower quaternary amines of temperature dissociates, membrane stability is poor have also restricted its development, become the break-through point in research.
For improving the performance of hydroxide ion exchange membrane, conventionally from improving ion concentration and constructing continuous regular ion transport passageSet about two aspects. Introduce and promote ion transport group, in lifting film, in ion concentration, significantly increased the ion of filmExchange capacity (IEC), has promoted the lifting of ionic conductance; Utilizing the close and distant pool of macromolecule that microphase-separated occurs forms regularIon transport passage, or by introducing intrinsic hole material, people constructs continuous ion transport passage, promotes ion transport,Improve the mechanical performance of film. Up to the present, chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film is for fuel cellHave no bibliographical information.
Summary of the invention
The object of the invention is to provide a kind of chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film and preparation and application.This hybridized film, for hydrogen-oxygen fuel cell, has higher ionic conduction and swelling resistance, and its preparation method process is simple.
The present invention proposes a kind of chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film, and this hybridized film thickness is 70～120μ m, is made up of the CNT of chloromethylation polyether-ether-ketone and imidazoles modification, imidazoles carbon nano tube and chloromethylation polyethersThe mass ratio of ether ketone is 0.05～0.2:1.
The preparation method of above-mentioned chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film, comprises following steps:
The preparation of step 1, chloromethylation reagent: adopt chloromethyl Octyl Ether to make chloromethylation reagent, synthetic method is: willRound-bottomed flask is placed in cryogenic thermostat reactive tank, under mechanical agitation, with (3～8): 1:(2～5) ratio add successively n-octyl alcohol, manyPolyformaldehyde and 40～80 order anhydrous chlorides of rase calcium powders, continue to pass into hydrogen chloride gas 2～5h, and after reaction finishes, leave standstill, filter,Get final product to obtain chloromethyl Octyl Ether.
The preparation of step 2, chloromethylation polyether-ether-ketone: in the concentrated sulfuric acid, add polyether-ether-ketone powder, wherein, polyether-ether-ketoneMass body volume concentrations is 10～25g/L, adds the chloromethyl Octyl Ether making in step 1 after fully stirring 3～6h, wherein,Chloromethyl Octyl Ether content accounts for 20～40% of mixed solution, reaction 20～160min after, by the mixture precipitation obtaining in mistakeMeasure in the cold deionized water of 5～10 times, and wash with water, the chloromethylation polyether-ether-ketone macromolecule of gained is dried for subsequent use;
The preparation of step 3, imidazoles carbon nano tube: by 3-(methacryloxypropyl) propyl trimethoxy silicane and multi-wall carbon nano-tubePipe joins in absolute ethyl alcohol taking volume mass ratio as the ratio of 1mL:1g, 3-(methacryloxypropyl) propyl trimethoxy silicaneWith the volume ratio of absolute ethyl alcohol be 1:100; Be placed in oil bath and react 24～48h, make to be modified with on multi-walled carbon nano-tubes carbon carbon twoKey; Vinyl imidazole, ethylene glycol dimethacrylate and the above-mentioned multi-walled carbon nano-tubes that is modified with carbon-carbon double bond are joinedIn acetonitrile-water mixed solution, multi-walled carbon nano-tubes, vinyl imidazole, ethylene glycol dimethacrylate and acetonitrile-water mix moltenThe mass volume ratio of liquid is 1:(4～15): (4～15): (300～800), after acetonitrile steams, centrifugation, the vinyl imidazole obtainingCoated multi-walled carbon nano-tubes is imidazoles carbon nano tube;
The preparation of step 4, hybridized film and film forming: take the chloromethylation polyether-ether-ketone making in step 2 and be dissolved in N, N-bis-In NMF, be configured to the mixed solution A that mass body volume concentrations is 0.1～0.3g/mL, under room temperature, stir 24h, same therewithTime, take imidazoles carbon nano tube that a certain amount of step 3 makes and join and in DMF, prepare quality volumeConcentration is the mixed solution B of 0.01～0.2g/mL, under room temperature, stirs 24h; Mixed solution A and mixed solution B are mixed allEven, obtain casting solution, casting solution is prolonged to stream on clean glass plate, at 60 DEG C of baking oven heating 12h, be adjusted to 80 DEG C,After 12h, take out film is taken off gently, finally obtain chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film.
By the above-mentioned chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film preparing for fuel cell hydroxide ionExchange membrane, under 25 DEG C of temperature, saturated humidity, hydroxide ion conductivity is 0.0174～0.0279Scm-1, swellbility phaseDecline 63.2%～78.3% than chloromethylation polyether-ether-ketone film.
Compared with prior art, the invention has the advantages that:
Preparation process of the present invention mainly comprises that preparing chloromethyl Octyl Ether makes chloromethylation reagent; By pungent to polyether-ether-ketone and chloromethylThe reaction of base ether, obtains chloromethylation polyether-ether-ketone; Prepare imidazoles modified carbon nano-tube; Imidazoles modified carbon nano-tube and chloromethaneBase polyether-ether-ketone blending obtains casting solution, makes this hybridized film through the tape casting. The preparation process operation letter of hybridized film of the present inventionSingle, green convenient, form crosslinked structure by chloromethylation polyether-ether-ketone and imidazoles carbon nano tube. This macromolecule-nothingMachine is intergranular crosslinked, and the one, increase substantially the swelling resistance of film, swellbility is compared pure film and has been declined 63.2 at 25 DEG C%～78.3%, makes film under hot and humid degree, still can keep good stability; The 2nd, cross-linked structure has been constructed continuous regularIon transport passage, promoted ion concentration, ionic conductance increases substantially, under 25 DEG C of temperature, saturated humidity,Hydroxide ion conductivity is 0.0174～0.0279Scm-1. Chloromethylation polyether-ether-ketone/imidazoles carbon nano tube the hydridization obtainingFilm is applied to hydrogen-oxygen fuel cell, possesses higher hydroxide ion conductivity and desirable swelling resistance.
Brief description of the drawings
Fig. 1 is the section SEM figure of the pure chloromethylation polyether-ether-ketone film (CPEEK) that makes of comparative example 1;
Fig. 2 is the section SEM figure of the CPEEK/PVICNT-5% hybridized film that makes of embodiment 1, wherein,CPEEK/PVICNT-5% represents imidazoles carbon nano tube (PVICNT) and chloromethylation polyether-ether-ketone (CPEEK)Mass ratio is 0.05:1;
Fig. 3 is the section SEM figure of the CPEEK/PVICNT-10% hybridized film that makes of embodiment 2, wherein,CPEEK/PVICNT-10% represents imidazoles carbon nano tube (PVICNT) and chloromethylation polyether-ether-ketone (CPEEK)Mass ratio is 0.1:1;
Fig. 4 is the section SEM figure of the CPEEK/PVICNT-15% hybridized film that makes of embodiment 3, wherein,CPEEK/PVICNT-15% represents imidazoles carbon nano tube (PVICNT) and chloromethylation polyether-ether-ketone (CPEEK)Mass ratio is 0.15:1;
Fig. 5 is the section SEM figure of the CPEEK/PVICNT-20% hybridized film that makes of embodiment 4, wherein,CPEEK/PVICNT-20% represents imidazoles carbon nano tube (PVICNT) and chloromethylation polyether-ether-ketone (CPEEK)Mass ratio is 0.2:1;
Fig. 6 is chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film of preparing under different imidazoles carbon nano tube loadingsHydroxide ion conductivity under different temperatures;
Fig. 7 is chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film of preparing under different imidazoles carbon nano tube loadingsSwellbility.
Detailed description of the invention
Tell about by the following examples detailed process of the present invention, it is the convenience in order to understand that embodiment is provided, and is never restrictionThe present invention.
Comparative example 1: prepare pure chloromethylation polyether-ether-ketone film (CPEEK).
The preparation of step 1, chloromethyl Octyl Ether: round-bottomed flask is placed in to cryogenic thermostat reactive tank, under mechanical agitation successivelyAdd 500mL n-octyl alcohol, 90g paraformaldehyde and 60 object 200g anhydrous chlorides of rase calcium powders, continue subsequently to pass into hydrogen chlorideGas 3h, constantly stirs in venting process, after reaction finishes, leaves standstill, filters, and obtains chloromethyl Octyl Ether.
The preparation of step 2, chloromethylation polyether-ether-ketone: add 1.5g polyether-ether-ketone powder in the 130mL concentrated sulfuric acid, fillDivide and stir the chloromethyl Octyl Ether that adds 50mL above-mentioned steps to make after 3h, after reaction 90min, the mixture obtaining is heavyForm sediment in the cold deionized water of excessive 8 times, and wash with water, the chloromethylation polyether-ether-ketone macromolecule of gained is dried for subsequent use.
The preparation of step 3, pure chloromethylation polyether-ether-ketone film: take 0.6g chloromethylation polyether-ether-ketone and be dissolved in 5mLN, N-In dimethyl formamide (DMF), under room temperature, stir 24h, the casting solution obtaining prolongs stream on clean glass plate, at 60 DEG CBaking oven heating 12h, is adjusted to 80 DEG C, after 12h, takes out film is taken off gently, finally obtains pure chloromethylation polyether-ether-ketone film,Be designated as CPEEK. Fig. 1 is the section SEM figure of this pure CPEEK film, and this film is entered under 25 DEG C of temperature, saturated humidityThe test of row ionic conductance, hydroxide ion conductivity is 0.0174Scm-1, swellbility is 77.8%.
Embodiment 1: preparation CPEEK/PVICNT-5% hybridized film, comprises following operating procedure:
The preparation of step 1, chloromethyl Octyl Ether: with comparative example 1;
The preparation of step 2, chloromethylation polyether-ether-ketone: with comparative example 1;
The preparation of step 3, imidazoles carbon nano tube: by the 3-of 0.5mL (methacryloxypropyl) propyl trimethoxy silicane andThe multi-walled carbon nano-tubes (MWCNTs) of 0.5g joins in the absolute ethyl alcohol of 50mL, is placed in oil bath and reacts 48h, makesOn MWCNTs, be modified with carbon-carbon double bond; The MWCNTs of 0.08g is joined in the acetonitrile-water mixed solution of 50mL,Then, add 0.6mL vinyl imidazole and 0.5mL ethylene glycol dimethacrylate. After acetonitrile steams, centrifugation,Obtain the coated MWCNTs of vinyl imidazole, be designated as PVICNT.
The preparation of step 4, hybridized film and film forming: the chloromethylation polyether-ether-ketone that takes preparation in 0.6g comparative example 1 is dissolved in5mLN, obtains mixed solution A in dinethylformamide (DMF), under room temperature, stir 24h, meanwhile, takes 0.03gThe PVICNT that step 3 makes, joins in 3mLDMF and obtains mixed solution B, under room temperature, stirs 24h. To mix moltenLiquid A and mixed solution B mix, and obtain casting solution, and this casting solution is prolonged to stream on clean glass plate, at 60 DEG CBaking oven heating 12h, is adjusted to 80 DEG C, after 12h, takes out film is taken off gently, finally obtains chloromethylation polyether-ether-ketone/imidazolesCarbon nano-tube hybridization film, is designated as CPEEK/PVICNT-5%.
Fig. 2 is the section SEM figure of this CPEEK/PVICNT-5% hybridized film, can find out, with right from Fig. 1 and Fig. 2The pure CPEEK film of ratio 1 is compared, the hybridized film after filling carbon nano-pipe, and without agglomeration, good interface compatibility. WillThis film carries out ionic conductance test under 25 DEG C of temperature, saturated humidity, and hydroxide ion conductivity is 0.0187Scm-1，Swellbility is 28.6%, and the pure film comparing in ratio 1 has declined 63.2%, and the introducing of visible cross-linked structure improves ionic conductionWhen rate, strengthen the stability of film.
Embodiment 2: preparation CPEEK/PVICNT-10% hybridized film, its preparation process is substantially the same manner as Example 1, noWith being only, in the preparation and film forming of step 4 hybridized film, while preparing mixed solution B, the step 3 adding makesThe amount of PVICNT changes 0.06g into by 0.03g, the chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film finally makingFor CPEEK/PVICNT-10%.
Fig. 3 is the section SEM figure of this CPEEK/PVICNT-10% hybridized film, can find out, with right from Fig. 1 and Fig. 3The pure CPEEK film of ratio 1 is compared, without agglomeration, and good interface compatibility. By this film in 25 DEG C of temperature, saturated wetUnder degree, carry out ionic conductance test, hydroxide ion conductivity is 0.0211Scm-1, swellbility is 18.5%, compares ratioPure CPEEK film in example 1 has declined 76.2%, when the introducing of visible cross-linked structure improves ionic conductance, has strengthenedThe stability of film.
Embodiment 3: preparation CPEEK/PVICNT-15% hybridized film, its preparation process is substantially the same manner as Example 1, noWith being only, in the preparation and film forming of step 4 hybridized film, while preparing mixed solution B, the step 3 adding makesThe amount of PVICNT changes 0.09g into by 0.03g, the chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film finally makingFor CPEEK/PVICNT-15%.
Fig. 4 is the section SEM figure of this CPEEK/PVICNT-15% hybridized film, with the pure CPEEK film phase of comparative example 1Ratio, the hybridized film after filling carbon nano-pipe, without agglomeration, good interface compatibility. By this film in 25 DEG C of temperature, saturatedUnder humidity, carry out ionic conductance test, hydroxide ion conductivity is 0.0262Scm-1, swellbility is 19.1%, comparesPure CPEEK film in ratio 1 has declined 75.5%.
Embodiment 4: preparation CPEEK/PVICNT-20% hybridized film, its preparation process is substantially the same manner as Example 1, noWith being only, in the preparation and film forming of step 4 hybridized film, while preparing mixed solution B, the step 3 adding makesThe amount of PVICNT changes 0.12g into by 0.03g, the chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film finally makingFor CPEEK/PVICNT-20%.
Fig. 5 is the section SEM figure of this CPEEK/PVICNT-20% hybridized film, with the pure CPEEK film phase of comparative example 1Ratio, the hybridized film after filling carbon nano-pipe, without agglomeration, good interface compatibility. By this hybridized film 25 DEG C of temperature,Under saturated humidity, carry out ionic conductance test, hydroxide ion conductivity is 0.0279Scm-1, swellbility is 16.9%, phaseDecline 78.3% than the pure CPEEK film in comparative example 1.
To sum up, by adjusting the loading of imidazoles carbon nano tube PVICNT, regulate and control imidazole group content in hybridized filmAnd the intergranular crosslinked action of macromolecule-inorganic, thereby affect ionic conduction performance and the stability of film. As seen from Figure 6,Along with the increase of imidazoles carbon nano tube loading, hybridized film hydroxide ion conductivity significantly improves, all higher than pure film,In Fig. 7, the introducing of imidazoles carbon nano tube has improved stability and the swelling resistance of hybridized film, and loading is more anti-swellingPerformance boost is more obvious, and the swellbility of film is lower, and the swellbility of hybridized film is all starkly lower than pure film.
The preparation process of hybridized film of the present invention is simple to operate, green convenient, and the chloromethylation polyether-ether-ketone/imidazoles carbon obtaining is receivedMitron hybridized film is applied to ion-exchange membrane fuel cell, possesses higher hydroxide ion conductivity and desirable anti-swellingEnergy.
Although in conjunction with figure, invention has been described above, the present invention is not limited to above-mentioned detailed description of the invention,Above-mentioned detailed description of the invention is only schematically, instead of restrictive, and those of ordinary skill in the art is in the present inventionEnlightenment under, in the situation that not departing from aim of the present invention, can also make a lot of distortion, these all belong to guarantor of the present inventionWithin protecting.
Claims (3)
1. chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film, is characterized in that: this hybridized film thickness is 70～120μ m, is made up of the CNT of chloromethylation polyether-ether-ketone and imidazoles modification, imidazoles carbon nano tube and chloromethylation polyethersThe mass ratio of ether ketone is 0.05～0.2:1.
2. a preparation method for chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film according to claim 1, itsBe characterised in that, comprise following steps:
The preparation of step 1, chloromethylation reagent:
Adopt chloromethyl Octyl Ether to make chloromethylation reagent, synthetic method is: round-bottomed flask is placed in to cryogenic thermostat reactive tank,Under mechanical agitation, with (3～8): 1:(2～5) ratio add successively n-octyl alcohol, paraformaldehyde and 40～80 order anhydrous chlorides of rase calcium powders,Continue to pass into hydrogen chloride gas 2～5h, after reaction finishes, leave standstill, filter, get final product to obtain chloromethyl Octyl Ether.
The preparation of step 2, chloromethylation polyether-ether-ketone:
In the concentrated sulfuric acid, add polyether-ether-ketone powder, wherein, polyether-ether-ketone mass body volume concentrations is 10～25g/L, fully stirsAfter 3～6h, add the chloromethyl Octyl Ether making in step 1, wherein, chloromethyl Octyl Ether content accounts for 20～40 of mixed solution%, after reaction 20～160min, in the cold deionized water of excessive 5～10 times, and washes the mixture precipitation obtaining with water,The chloromethylation polyether-ether-ketone macromolecule of gained is dried for subsequent use;
The preparation of step 3, imidazoles carbon nano tube:
3-(methacryloxypropyl) propyl trimethoxy silicane and multi-walled carbon nano-tubes are added with the volume mass ratio of 1mL:1gIn absolute ethyl alcohol, the volume ratio of 3-(methacryloxypropyl) propyl trimethoxy silicane and absolute ethyl alcohol is 1:100; Be placed in oilIn bath, react 24～48h, make to be modified with on multi-walled carbon nano-tubes carbon-carbon double bond; By vinyl imidazole, ethylene glycol dimethyl propyleneAcid esters and the above-mentioned multi-walled carbon nano-tubes that is modified with carbon-carbon double bond join in acetonitrile-water mixed solution, multi-walled carbon nano-tubes, secondThe mass volume ratio of thiazolinyl imidazoles, ethylene glycol dimethacrylate and acetonitrile-water mixed solution is1:(4～15): (4～15): (300～800), after acetonitrile steams, centrifugation, the coated multi-wall carbon nano-tube of vinyl imidazole obtainingPipe is imidazoles carbon nano tube;
The preparation of step 4, hybridized film and film forming:
Taking the chloromethylation polyether-ether-ketone making in step 2 is dissolved in and in DMF, is configured to quality volumeConcentration is the mixed solution A of 0.1～0.3g/mL, under room temperature, stirs 24h, meanwhile, takes a certain amount of step 3 and makesImidazoles carbon nano tube join and in DMF, prepare the mixing that mass body volume concentrations is 0.01～0.2g/mLSolution B, stirs 24h under room temperature; Mixed solution A and mixed solution B are mixed, obtain casting solution, by casting solutionProlong stream on clean glass plate, at 60 DEG C of baking oven heating 12h, be adjusted to 80 DEG C, after 12h, take out film is taken off gently,Finally obtain chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film.
3. an application for chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film, is characterized in that, by claim 2Chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film that described preparation method makes is handed over for fuel cell hydroxide ionChange film, under 25 DEG C of temperature, saturated humidity, hydroxide ion conductivity is 0.0174～0.0279Scm-1, swellbility is comparedChloromethylation polyether-ether-ketone film has declined 63.2%～78.3%.
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| 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 |
| CN109809539A (en) * | 2019-03-25 | 2019-05-28 | 江苏美淼环保科技有限公司 | Modified anion exchange membrane and preparation method thereof and membrane capacitance deionizer |
| CN113235200A (en) * | 2021-05-19 | 2021-08-10 | 江阴市薪天纱业有限公司 | Spinning manufacturing process of rung-free superfine chenille knitted fabric |
| CN114773753A (en) * | 2022-04-29 | 2022-07-22 | 华南理工大学 | Polyether-ether-ketone-polyvinylidene fluoride composite membrane and preparation method and application thereof |
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| CN108976169A (en) * | 2018-08-30 | 2018-12-11 | 河北工业大学 | A kind of glyoxaline ion liquid and its preparation method and application |
| 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 |
| CN109809539A (en) * | 2019-03-25 | 2019-05-28 | 江苏美淼环保科技有限公司 | Modified anion exchange membrane and preparation method thereof and membrane capacitance deionizer |
| CN113235200A (en) * | 2021-05-19 | 2021-08-10 | 江阴市薪天纱业有限公司 | Spinning manufacturing process of rung-free superfine chenille knitted fabric |
| CN113235200B (en) * | 2021-05-19 | 2023-02-21 | 江阴市薪天纱业有限公司 | Spinning manufacturing process of rung-free superfine chenille knitted fabric |
| CN114773753A (en) * | 2022-04-29 | 2022-07-22 | 华南理工大学 | Polyether-ether-ketone-polyvinylidene fluoride composite membrane and preparation method and application thereof |
| CN114773753B (en) * | 2022-04-29 | 2023-05-02 | 华南理工大学 | Polyether-ether-ketone-polyvinylidene fluoride composite membrane and preparation method and application thereof |
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