CN117431586A - Preparation method of modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water - Google Patents
Preparation method of modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000012528 membrane Substances 0.000 title claims abstract description 47
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 32
- 239000011521 glass Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000009832 plasma treatment Methods 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 15
- 238000007790 scraping Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229920005596 polymer binder Polymers 0.000 claims abstract description 8
- 239000002491 polymer binding agent Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 43
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 34
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 28
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 230000001112 coagulating effect Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- 230000003014 reinforcing effect Effects 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000013557 residual solvent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 6
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229940069328 povidone Drugs 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000000614 phase inversion technique Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- -1 polyacetylimide Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001479434 Agfa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FJMYXUFOLMQNLL-UHFFFAOYSA-N propan-1-ol;prop-2-enoic acid Chemical compound CCCO.OC(=O)C=C FJMYXUFOLMQNLL-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DUZHCFGUSIJGMU-UHFFFAOYSA-N toluene;3-triethoxysilylpropan-1-amine Chemical compound CC1=CC=CC=C1.CCO[Si](OCC)(OCC)CCCN DUZHCFGUSIJGMU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparation method of a modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water. The invention carries out one-pot modification on inorganic nano particles, then mixes polymer binder, modified inorganic nano particles, pore-forming agent and organic solvent to obtain casting solution, carries out plasma treatment on a porous supporting layer, fixes the treated porous supporting layer on a glass plate, pours the casting solution on the supporting layer on one side of the glass plate, scrapes a film on a grid in one step by using a film scraper, and obtains the supported porous diaphragm by a steam-induced phase inversion method and a liquid-induced phase inversion method. According to the invention, the dispersibility of the inorganic nano particles in the membrane is improved by carrying out surface grafting modification on the inorganic nano particles, the hydrophilicity and the compatibility with slurry are improved by carrying out plasma treatment on the supporting layer, and the nano composite membrane is efficiently prepared by a one-step membrane scraping process and a phase inversion method, so that the membrane has high hydrophilicity, pore uniformity and high mechanical strength.
Description
Technical Field
The invention relates to a preparation method of an alkaline electrolyzed water diaphragm, in particular to a preparation method of a diaphragm with high hydrophilicity, mechanical property, uniform and stable pore.
Background
The proportion of renewable energy is continuously improved, but the current wind power, photovoltaic and other energy sources have intermittent and unstable problems, so that the direct utilization is difficult, the energy sources can be finally converted into stable and continuous hydrogen energy, and meanwhile, the hydrogen energy has the advantages of being green, clean and efficient, so that the method has been widely focused and studied. At present, in the hydrogen production technology, fossil energy hydrogen production takes the main stream, but carbon emission still occurs in the hydrogen production process, so that the green hydrogen cannot be truly achieved; the zero emission can be realized by preparing hydrogen through the water electrolysis hydrogen production technology, and the method is the main stream direction for preparing green hydrogen in the future.
The current water electrolysis hydrogen production technology is mainly divided into an alkaline water electrolysis hydrogen production technology, a proton exchange membrane water electrolysis hydrogen production technology and a solid oxide water electrolysis technology, and the alkaline water electrolysis technology is the earliest water electrolysis hydrogen production technology, and is simple to operate, does not need to use a noble metal electrode, has relatively good stability and low cost, can be used for large-scale hydrogen production occasions, and has been widely researched by a plurality of experts in recent years.
The diaphragm plays an important role in the alkaline water electrolysis technology, and the good diaphragm needs to have the following characteristics: (1) Good hydrophilicity, water permeability and higher porosity, can ensure mass transfer of electrolyte, has lower surface resistance and reduces loss; (2) Good gas barrier property, smaller pore diameter, no penetration of hydrogen and oxygen through the membrane, and high purity of produced gas; (3) Good chemical stability and mechanical stability, and can maintain performance for a long time in an alkaline environment under certain pressure.
The asbestos diaphragm is the earliest alkaline electrolytic water diaphragm, but has higher resistance due to poor conductivity, is easy to be corroded and swelled by alkaline electrolyte, has carcinogenicity to human body, and is gradually replaced by other separation materials; polyphenylene sulfide is also a main alkaline electrolytic water diaphragm, but the hydrophilicity of the polyphenylene sulfide is poor, larger resistance can be generated in the use process, the loss is larger, and the air tightness is still to be further improved; thus, the hot spot of current research is mainlyThe membrane has the advantages of being concentrated in an organic-inorganic composite membrane, combining the advantages of organic matters and inorganic matters, being capable of ensuring that the membrane has good alkali resistance and corrosion resistance, good hydrophilicity and certain mechanical properties, and the Zirfon series membrane of AGFA company has a leading position in the industry at present, and is composed of 20 percent polysulfone and 80 percent ZrO 2 The composition has higher current density and better stability, but is expensive.
The alkaline electrolytic water diaphragm used in the current market has high inorganic content, which inevitably has some problems, the higher inorganic content leads to poorer mechanical property, the diaphragm is more brittle, and the continuous and stable operation of the electrolytic water device is influenced; the alkali loss is high, and inorganic particles in the diaphragm are easy to fall off in the soaking of alkali liquor for a long time; poor dispersibility and easy agglomeration, so that the diaphragm becomes uneven and the performance is affected. Therefore, there is a need to develop an alkaline electrolyte membrane which has high hydrophilicity, mechanical properties, uniform pores and stability.
Disclosure of Invention
The invention aims to solve one or more problems of the existing alkaline electrolytic water diaphragm, and provides a preparation method of the alkaline electrolytic water diaphragm with high hydrophilicity, mechanical property, uniformity and stability.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a nano-composite diaphragm for alkaline electrolysis of water is prepared through modifying inorganic nanoparticles by one-pot method, mixing polymer adhesive, modified inorganic nanoparticles, pore-forming agent and organic solvent to obtain a film-casting liquid, plasma treating porous supporting layer, fixing it on glass plate, pouring it on the supporting layer at one side of glass plate, scraping film on grid by a scraper, and steam-induced phase inversion and liquid-induced phase inversion.
The surface interface chemical grafting and modification are carried out on the inorganic nano particles by selecting a proper modifier, functional groups are introduced, and the hydrophilia and the compatibility of a casting solution matrix are improved by further carrying out plasma treatment on the supporting layer, so that the agglomeration phenomenon in the processing process is avoided. The system researches the addition amount, the combination mode and the dispersivity of the inorganic nano particles, optimizes the dispersion capacity and the addition mode of the inorganic nano particles in the nano composite membrane, and realizes the high-efficiency hydrophilic and mechanical enhancement effect on the nano composite membrane material.
A method for preparing a modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water, as shown in figure 1, comprising the following steps:
(1) Preparation of modified inorganic nanoparticles:
adding inorganic nano particles into a modifying solvent containing a modifying agent, stirring at a certain stirring speed, heating to a certain temperature in the process, refluxing, centrifuging, ultrasonic treating, suction filtering, repeatedly washing, and drying at a constant temperature for a period of time to obtain the modified inorganic nano particles. Wherein, the mass consumption of the modifier is 2-200% of the mass consumption of the inorganic nano particles; the mass consumption of the modifier is 0.1-80% of the mass consumption of the modifying solvent; wherein the stirring speed is 200-800 rpm; the heating temperature is 60-150 ℃; the reflux time is 0.5-6 h; the centrifugation time is 10-60 min; the ultrasonic time is 5-30 min; the drying temperature is 80-120 ℃; the drying time is 2-5 h.
(2) Preparing a casting solution:
adding polymer binder into film-making solvent in batches, stirring at 200-800 rpm and 20-60 deg.c, adding modified inorganic nanometer particle and pore-forming agent successively, stirring for 4-30 hr, regulating stirring speed to 40-80 rpm, degassing and eliminating bubble for 1-2 hr, and final ultrasonic treatment of the slurry for 0.5-1 hr to obtain milky film casting liquid. The mass ratio of the polymer binder to the inorganic nano particles is (1:9) - (2:3), preferably (1:8.5) - (1:4), the mass ratio of the film-forming solvent in the film casting liquid is 40% -60%, preferably 45% -55%, and the mass ratio of the pore-foaming agent in the film casting liquid is 0.1% -10%, preferably 0.5% -3%.
(3) Preparation of a nanocomposite separator:
the porous enhancement layer is processed by plasma, wherein the plasma processing pressure is 10 Pa to 50Pa, the power is 30W to 70W, the processing time is 90 s to 180s, and the distance between the polar plates is 1.5 cm to 2.5cm. Placing the porous reinforcing layer subjected to plasma treatment on an ultra-clean glass flat plate after hot pressing and flattening, fixing by a clamp, pouring casting film liquid on a supporting layer on one side of the glass flat plate, scraping a wet film with the thickness of 500-1000 mu m on the porous reinforcing layer by a film scraper, fully soaking the porous reinforcing layer, standing for 10-30 s in an air atmosphere, immersing the porous reinforcing layer in a coagulating bath at the temperature of 0-60 ℃ for 10-30 min, taking out the porous reinforcing layer from the coagulating bath after phase transformation, immersing in water for a plurality of times, cleaning residual solvents, naturally airing, and cutting to obtain the composite diaphragm for alkaline electrolyzed water.
The polymer binder is one or more of polysulfone, polyethersulfone, polyphenylsulfone, polystyrene, polyacetylimide, polyethylene and polypropylene, wherein polysulfone and polyethersulfone are preferable, and the molecular weight is 20000-100000, preferably 40000-80000.
The inorganic nano particles are selected from one or more of nano zirconium oxide, nano titanium oxide, nano zinc oxide, nano copper oxide, nano aluminum oxide, nano cerium oxide and nano silicon oxide.
The modifier is selected from one of polyethylene glycol, diethanolamine, acrylic acid, adipic acid and aminopropyl triethoxysilane.
The particle size of the inorganic nanoparticles is 0.05-1 μm, preferably 0.2-0.4 μm.
The pore-forming agent is one or more selected from polyvinylpyrrolidone, povidone, polyurethane and talcum powder, wherein polyvinylpyrrolidone is preferred, and the molecular weight is 4000-80000, preferably 8000-58000.
The film forming solvent is selected from one or more of N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP), N-butyl pyrrolidone (NBP), dimethyl sulfoxide (DMSO), acetone, xylene, toluene, N-Dimethylformamide (DMF), preferably one of N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP) and N-butyl pyrrolidone (NBP).
The porous reinforcing layer adopts one of polyphenylene sulfide mesh, polyphenylene sulfide non-woven fabric, polyphenylene sulfide fiber paper and polyether-ether-ketone mesh, the mesh thickness is 50-1000 mu m, the mesh number is 20-300 mu m, wherein the thickness is preferably 100-300 mu m, and the mesh number is preferably 40-150 mu.
The coagulating bath is water or a mixture of water and a film-forming solvent, wherein the mass fraction of the water is 50-100%.
Compared with the prior art, the invention has the excellent effects that:
(1) The inorganic nano particles are subjected to surface modification, so that the inorganic nano particles are not easy to agglomerate, have better dispersibility, and improve the overall performance and uniform stability of the film;
(2) The porous enhancement layer is subjected to plasma treatment, so that the porous enhancement layer has better hydrophilicity, and simultaneously has better adhesion and compatibility with coating solution, thereby improving the production efficiency and reducing the diaphragm loss;
(3) The preparation method has the advantages of simple film-forming process, wide application range, and good high hydrophilicity, mechanical property, uniformity and stability, so that the preparation method has wide application prospect.
Drawings
FIG. 1 is a process flow for preparing a nanocomposite separator.
Fig. 2 is a diagram showing the effect of the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments, but the scope of the invention is not limited thereto:
example 1
Adding 15g of nano zirconia particles into 25g of ethanol solution of diethanolamine, stirring and heating to 100 ℃ at 300rpm, refluxing for 3 hours, centrifuging for 20 minutes, carrying out ultrasonic treatment for 10 minutes, carrying out suction filtration, washing for 3 times, and drying at the constant temperature of 100 ℃ for 3 hours to obtain modified zirconia particles.
3g of polysulfone is added into 15g N-methyl pyrrolidone twice, 12g of modified nano zirconia particles are added into the solution, 0.3g of polyvinylpyrrolidone is added, stirring is carried out at room temperature for 16 hours to enable the polyvinylpyrrolidone to be fully dissolved and dispersed, the stirring speed is 300rpm, the stirring speed is adjusted to 60rpm, stirring is carried out for 2 hours to degas and remove bubbles, and the obtained slurry is subjected to ultrasonic treatment for 1 hour.
100 mu m thick and 50 meshes of polyphenylene sulfide are placed in a reaction chamber of a low-temperature plasma instrument, the reaction chamber is vacuumized, an oxygen inlet valve is opened, the pressure is regulated to 20Pa, the power is 50W, and the treatment time is 120s. Placing the polyphenylene sulfide grid subjected to plasma treatment on a glass flat plate, pressing to be flat, scraping a wet film of 750 mu m on the glass flat plate by a film scraper, fully soaking the polyphenylene sulfide grid, standing in air for 15s, carrying out gas-phase induced phase separation, overturning the glass flat plate, placing in a coagulating bath of pure water at 25 ℃ to carry out immersed precipitation phase conversion, taking out the solidified nano composite membrane after 10min, washing 3 times by pure water, washing off residual solvent, placing in room temperature, and naturally airing to obtain the nano composite membrane for alkaline electrolytic water.
Comparative example 1
3g of polysulfone is added into 15g N-methyl pyrrolidone twice, 12g of nano zirconia particles are added into the solution, 0.3g of polyvinylpyrrolidone is added, stirring is carried out at room temperature for 16 hours to fully dissolve and disperse, the stirring speed is 300rpm, the stirring speed is adjusted to 60rpm, stirring is carried out for 2 hours to degas and remove bubbles, and the obtained slurry is subjected to ultrasonic treatment for 1 hour.
100 mu m thick and 50 meshes of polyphenylene sulfide are placed in a reaction chamber of a low-temperature plasma instrument, the reaction chamber is vacuumized, an oxygen inlet valve is opened, the pressure is regulated to 20Pa, the power is 50W, and the treatment time is 120s. Placing the polyphenylene sulfide grid subjected to plasma treatment on a glass flat plate, pressing to be flat, scraping a wet film of 750 mu m on the glass flat plate by a film scraper, fully soaking the polyphenylene sulfide grid, standing in air for 15s, carrying out gas-phase induced phase separation, overturning the glass flat plate, placing in a coagulating bath of pure water at 25 ℃ to carry out immersed precipitation phase conversion, taking out the solidified nano composite membrane after 10min, washing 3 times by pure water, washing off residual solvent, placing in room temperature, and naturally airing to obtain the nano composite membrane for alkaline electrolytic water.
Comparative example 2
Adding 15g of nano zirconia particles into 25g of ethanol solution of diethanolamine, stirring and heating to 100 ℃ at 300rpm, refluxing for 3 hours, centrifuging for 20 minutes, carrying out ultrasonic treatment for 10 minutes, carrying out suction filtration, washing for 3 times, and drying at the constant temperature of 100 ℃ for 3 hours to obtain modified zirconia particles.
3g of polysulfone is added into 15g N-methyl pyrrolidone twice, 12g of modified nano zirconia particles are added into the solution, 0.3g of polyvinylpyrrolidone is added, stirring is carried out at room temperature for 16 hours to enable the polyvinylpyrrolidone to be fully dissolved and dispersed, the stirring speed is 300rpm, the stirring speed is adjusted to 60rpm, stirring is carried out for 2 hours to degas and remove bubbles, and the obtained slurry is subjected to ultrasonic treatment for 1 hour.
Placing a polyphenylene sulfide grid with the thickness of 100 mu m and the mesh of 50 mu on a glass flat plate, pressing to be flat, scraping a wet film with the thickness of 750 mu m on the glass flat plate by a film scraper, fully soaking the polyphenylene sulfide grid, standing for 15s in air, carrying out gas-phase induced phase separation, overturning the glass flat plate, placing the glass flat plate in a coagulating bath of pure water with the temperature of 25 ℃ to carry out immersed precipitation phase conversion, taking out the solidified nano composite membrane after 10min, washing 3 times by pure water, washing off residual solvent, placing the nano composite membrane at room temperature, and naturally airing to obtain the nano composite membrane for alkaline electrolytic water.
Example 2
15g of nano zirconia particles are added into 18g of toluene saturated solution of adipic acid, the mixture is heated to 110 ℃ while being stirred, the mixture is refluxed for 1h, and the mixture is centrifuged for 30min, ultrasonically treated for 20min, suction filtered and washed for 3 times, and dried at a constant temperature of 100 ℃ for 3h to obtain the modified zirconia particles.
3g of polysulfone is added into 15g N-methyl pyrrolidone twice, 12g of modified nano zirconia particles are added into the solution, 1.5g of polyvinylpyrrolidone is added, stirring is carried out for 12 hours at room temperature to enable the polyvinylpyrrolidone to be fully dissolved and dispersed, the stirring speed is 400rpm, the stirring speed is adjusted to 60rpm, stirring is carried out for 2 hours, degassing and defoaming are carried out, and then the obtained slurry is subjected to ultrasonic treatment for 1 hour.
200 mu m thick and 50 meshes of polyphenylene sulfide are placed in a reaction chamber of a low-temperature plasma instrument, the reaction chamber is vacuumized, an oxygen inlet valve is opened, the pressure is regulated to 50Pa, the power is 50W, and the treatment time is 120s. Placing the polyphenylene sulfide grid subjected to plasma treatment on a glass flat plate, pressing to be flat, scraping a wet film of 750 mu m on the glass flat plate by a film scraping device, fully soaking the polyphenylene sulfide grid, standing in air for 30s, carrying out gas-phase induced phase separation, overturning the glass flat plate, placing in a coagulating bath of pure water at 10 ℃ to carry out immersion precipitation phase conversion, taking out the solidified composite membrane after 10min, washing 3 times by pure water, washing away residual solvent, placing in room temperature, and naturally airing to obtain the composite membrane for alkaline electrolyzed water.
Example 3
15g of nano zirconia particles are added into 50ml of 10% aminopropyl triethoxysilane toluene solution, heated to 90 ℃ under stirring at 300rpm, refluxed for 1h, centrifuged for 30min, ultrasonic for 20min, filtered, washed for 3 times, and dried at a constant temperature of 100 ℃ for 3h to obtain modified zirconia particles.
Adding 2g of polysulfone into 20g N-methyl pyrrolidone twice, adding 18g of modified nano zirconia particles into the solution, adding 0.2g of polyvinylpyrrolidone, stirring at room temperature for 12 hours to enable the polyvinylpyrrolidone to be fully dissolved and dispersed, adjusting the stirring rate to be 60rpm, stirring for 2 hours to degas and debubble, and carrying out ultrasonic treatment on the obtained slurry for 1 hour.
100 mu m thick and 150 meshes of polyphenylene sulfide are placed in a reaction chamber of a low-temperature plasma instrument, the reaction chamber is vacuumized, an oxygen inlet valve is opened, the pressure is regulated to 20Pa, the power is 30W, and the treatment time is 120s. Placing the polyphenylene sulfide grid subjected to plasma treatment on a glass flat plate, pressing to be flat, scraping a 500 mu m wet film on the glass flat plate by a film scraping device, fully soaking the polyphenylene sulfide grid, standing in air for 30s, carrying out gas-phase induced phase separation, overturning the glass flat plate, placing in a coagulating bath of pure water at 25 ℃ for carrying out immersion precipitation phase conversion, taking out the solidified composite membrane after 30min, washing 3 times by pure water, washing out residual solvent, placing in room temperature, and naturally airing to obtain the composite membrane for alkaline electrolyzed water.
Example 4
Adding 15g of nano zirconia particles into 10g of polyethylene glycol aqueous solution, stirring and heating to 95 ℃ at 400rpm, refluxing for 2 hours, centrifuging for 20 minutes, carrying out ultrasonic treatment for 10 minutes, carrying out suction filtration, washing for 3 times, and drying at a constant temperature of 100 ℃ for 3 hours to obtain modified zirconia particles.
3g of polysulfone is added into 20g N-methyl pyrrolidone twice, 12g of modified nano zirconia particles are added into the solution, 0.5g of polyvinylpyrrolidone is added, stirring is carried out for 24 hours at room temperature to enable the polyvinylpyrrolidone to be fully dissolved and dispersed, the stirring speed is 300rpm, the stirring speed is adjusted to 60rpm, stirring is carried out for 2 hours, degassing and defoaming are carried out, and then the obtained slurry is subjected to ultrasonic treatment for 1 hour.
100 mu m thick and 150 meshes of polyphenylene sulfide are placed in a reaction chamber of a low-temperature plasma instrument, the reaction chamber is vacuumized, an oxygen inlet valve is opened, the pressure is regulated to 20Pa, the power is 50W, and the treatment time is 180s. Placing the polyphenylene sulfide grid subjected to plasma treatment on a glass flat plate, pressing to be flat, scraping a 500 mu m wet film on the glass flat plate by a film scraping device, fully soaking the polyphenylene sulfide grid, standing in air for 15s, carrying out gas-phase induced phase separation, overturning the glass flat plate, placing in a coagulating bath of pure water at 40 ℃ to carry out immersed precipitation phase conversion, taking out the solidified composite membrane after 20min, washing 3 times by pure water, washing out residual solvent, placing in room temperature, and naturally airing to obtain the composite membrane for alkaline electrolyzed water.
Example 5
15g of nano zirconia particles are added into 25g of acrylic acid propanol solution, stirred and heated to 100 ℃ at 400rpm, refluxed for 3 hours, centrifuged for 20 minutes, ultrasonically treated for 10 minutes, suction filtered, washed for 3 times, and dried at a constant temperature of 100 ℃ for 3 hours to obtain modified zirconia particles.
3g of polysulfone is added into 20g N-methyl pyrrolidone twice, 17g of modified nano zirconia particles are added into the solution, 0.8g of polyvinylpyrrolidone is added, stirring is carried out for 24 hours at room temperature to enable the polyvinylpyrrolidone to be fully dissolved and dispersed, the stirring speed is 400rpm, the stirring speed is adjusted to 60rpm, stirring is carried out for 2 hours, degassing and defoaming are carried out, and then the obtained slurry is subjected to ultrasonic treatment for 1 hour.
200 mu m thick and 50 meshes of polyphenylene sulfide are placed in a reaction chamber of a low-temperature plasma instrument, the reaction chamber is vacuumized, an oxygen inlet valve is opened, the pressure is regulated to 50Pa, the power is 30W, and the treatment time is 150s. Placing the polyphenylene sulfide grid subjected to plasma treatment on a glass flat plate, pressing to be flat, scraping a wet film of 750 mu m on the glass flat plate by a film scraper, fully soaking the polyphenylene sulfide grid, standing for 15s in air, carrying out gas-phase induced phase separation, overturning the glass flat plate, placing in a coagulating bath of pure water at 15 ℃ to carry out immersed precipitation phase conversion, taking out the solidified nano composite membrane after 10min, washing 3 times by pure water, washing off residual solvent, placing in room temperature, and naturally airing to obtain the nano composite membrane for alkaline electrolytic water.
Table 1 comparison of test results for examples 1 to 5 and comparative examples 1 to 2
| Time to full water absorption | Mechanical properties | Alkali absorption rate | Surface resistance | |
| Example 1 | 18s | Good (good) | 107.39％ | 1.062Ω·cm2 |
| Comparative example 1 | 27s | Good (good) | 109.29％ | 1.563Ω·cm2 |
| Comparative example 2 | 24s | Preferably, it is | 115.42％ | 1.473Ω·cm2 |
| Example 2 | 14s | Preferably, it is | 152.44％ | 0.872Ω·cm2 |
| Example 3 | 9s | Is relatively fragile | 132.22％ | 0.534Ω·cm2 |
| Example 4 | 15s | Good (good) | 127.16％ | 0.628Ω·cm2 |
| Example 5 | 5s | Good (good) | 118.99％ | 0.742Ω·cm2 |
As shown in fig. 1 and 2, the surface resistance property of example 1 was significantly improved as compared with comparative example 1 without modification of the inorganic nanoparticles and as compared with comparative example 2 with plasma treatment. In example 4, the hydrophilicity and the dispersibility of the inorganic nano particles are obviously improved by modifying the inorganic nano particles with polyethylene glycol, and the content of the inorganic nano particles in the separator is up to 80 percent, so that the separator has the best surface resistance performance due to the thinner thickness.
In summary, the invention improves the dispersibility of inorganic nano particles in the membrane by carrying out surface grafting modification, improves the hydrophilicity and the compatibility with slurry by carrying out plasma treatment on the supporting layer, and finally prepares the nano composite membrane with high efficiency by a one-step membrane scraping process and a phase inversion method.
Claims (10)
1. The preparation method of the modified nano composite membrane for the high-hydrophilicity alkaline electrolyzed water is characterized by comprising the following steps of:
(1) Preparation of modified inorganic nanoparticles:
adding inorganic nano particles into a modifying solvent containing a modifying agent, stirring at a certain stirring speed, heating to a certain temperature in the process, refluxing, centrifuging, ultrasonic treating, suction filtering, repeatedly washing, and drying at a constant temperature for a period of time to obtain modified inorganic nano particles;
(2) Preparing a casting solution:
adding a polymer binder into a film-making solvent in batches, stirring at a speed of 200-800 rpm and a temperature of 20-60 ℃, then gradually adding modified inorganic nano particles and a pore-forming agent in sequence, stirring for 4-30 h, adjusting the stirring speed to 40-80 rpm, performing degassing and bubble removal treatment for 1-2 h, and finally performing ultrasonic treatment on the obtained slurry for 0.5-1 h to obtain milky film casting liquid;
(3) Preparation of a nanocomposite separator:
the porous reinforcing layer is subjected to plasma treatment, the porous reinforcing layer after the plasma treatment is subjected to hot pressing and flattening, then is placed on an ultra-clean glass flat plate, is fixed by a clamp, is poured on a supporting layer on one side of the glass flat plate, is scraped with a film scraping device to obtain a wet film with the thickness of 500-1000 mu m, fully infiltrates the porous reinforcing layer, stands for 10-30 s in an air atmosphere, is immersed in a coagulating bath at the temperature of 0-60 ℃ for 10-30 min, is taken out from the coagulating bath after phase conversion, is immersed in water for a plurality of times, is used for cleaning residual solvents, is naturally dried, and is cut to obtain the composite diaphragm for alkaline electrolyzed water.
2. The preparation method of the modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water, which is characterized in that the mass usage of the modifier is 2-200% of the mass usage of inorganic nano particles; the mass consumption of the modifier is 0.1-80% of the mass consumption of the modifying solvent; wherein the stirring speed is 200-800 rpm; the heating temperature is 60-150 ℃; the reflux time is 0.5-6 h; the centrifugation time is 10-60 min; the ultrasonic time is 5-30 min; the drying temperature is 80-120 ℃; the drying time is 2-5 h.
3. The preparation method of the modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water, which is disclosed in claim 1, is characterized in that the mass ratio of the polymer binder to the inorganic nano particles is (1:9) - (2:3), the mass ratio of the film forming solvent in the film casting solution is 40% -60%, and the mass ratio of the pore-forming agent in the film casting solution is 0.1% -10%.
4. The method for preparing the modified nanocomposite membrane for highly hydrophilic alkaline electrolyzed water according to claim 1 or 2, wherein the mass ratio of the polymer binder to the inorganic nanoparticles is (1:8.5) - (1:4), the mass ratio of the membrane-forming solvent in the membrane casting solution is 45% -55%, and the mass ratio of the pore-forming agent in the membrane casting solution is 0.5% -3%.
5. The method for preparing the modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water according to claim 4, which is characterized in that the plasma treatment pressure is 10-50 Pa, the power is 30-70W, the treatment time is 90-180 s, and the plate distance is 1.5-2.5 cm.
6. The method for preparing the modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water according to claim 5, wherein the polymer binder is polysulfone and polyether sulfone, and the molecular weight is 20000-100000.
7. The method for preparing a modified nanocomposite membrane for highly hydrophilic alkaline electrolyzed water according to claim 5 or 6, wherein the inorganic nanoparticles are one or more selected from the group consisting of nano zirconia, nano titania, nano zinc oxide, nano copper oxide, nano alumina, nano cerium oxide, and nano silicon oxide; the modifier is selected from one of polyethylene glycol, diethanolamine, acrylic acid, adipic acid and aminopropyl triethoxysilane; and the particle size of the inorganic nano particles is 0.05-1 mu m.
8. The method for preparing the modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water according to claim 5 or 6, wherein the pore-forming agent is one or more selected from polyvinylpyrrolidone, povidone, polyurethane and talcum powder, and has a molecular weight of 4000-80000.
9. The method for preparing a modified nanocomposite membrane for highly hydrophilic alkaline electrolyzed water according to claim 5 or 6, wherein the membrane-forming solvent is one selected from the group consisting of N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), and N-butylpyrrolidone (NBP); the coagulating bath is water or a mixture of water and a film-forming solvent, wherein the mass fraction of the water is 50% -100%.
10. The method for preparing the modified nano composite membrane for high-hydrophilicity alkaline electrolyzed water according to claim 5 or 6, wherein the porous reinforcing layer adopts one of polyphenylene sulfide mesh, polyphenylene sulfide non-woven fabric, polyphenylene sulfide fiber paper and polyether ether ketone mesh, the mesh thickness is 100-300 mu m, and the mesh number is 40-150 mesh.
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| CN117721498B (en) * | 2024-02-07 | 2024-05-07 | 宁波中科氢易膜科技有限公司 | Preparation method of organic-inorganic hybrid ion composite membrane |
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