CN116832631A - Carbonized ceramic conductive film and preparation method thereof - Google Patents
Carbonized ceramic conductive film and preparation method thereof Download PDFInfo
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- CN116832631A CN116832631A CN202310824784.9A CN202310824784A CN116832631A CN 116832631 A CN116832631 A CN 116832631A CN 202310824784 A CN202310824784 A CN 202310824784A CN 116832631 A CN116832631 A CN 116832631A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 45
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 11
- 238000005345 coagulation Methods 0.000 claims description 11
- 230000015271 coagulation Effects 0.000 claims description 11
- 239000002861 polymer material Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007790 scraping Methods 0.000 claims description 7
- -1 polypropylene Polymers 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 16
- 239000002243 precursor Substances 0.000 abstract description 4
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 230000004907 flux Effects 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 5
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
- B01D71/421—Polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a carbonized ceramic conductive film and a preparation method thereof, and relates to the technical field of conductive films. According to the invention, a phase inversion technology is adopted to firstly dissolve polyacrylonitrile and perform mixed phase inversion on ceramic particles to prepare a polyacrylonitrile polymer ceramic film precursor, and then the polyacrylonitrile polymer in the ceramic film precursor is subjected to high-temperature carbonization after low-temperature pre-oxidation to convert the polyacrylonitrile polymer into a graphite carbon structure with high conductivity, so that the carbonized ceramic conductive film is prepared. The preparation method can adjust the membrane structure and the membrane pore size, and simultaneously obviously reduce the resistance of the membrane and ensure that the membrane has good mechanical property and stability.
Description
Technical Field
The invention relates to the technical field of conductive films, in particular to a carbonized ceramic conductive film and a preparation method thereof.
Background
Traditional nanofiltration and reverse osmosis membranes have good interception effect on small-size pollutants but low permeation flux, and traditional microfiltration ultrafiltration has high permeation flux but is difficult to intercept the small-size pollutants. The reason is that the small-size pollutants mostly have different charges, the conductive film can introduce charges into the surface and the inside of the film through an external power supply, the interception capability of the film to the small-molecular pollutants is improved through enhancing the electrostatic acting force between the film and the small-molecular pollutants, the Trade-off effect between the interception rate of the film to the pollutants and the permeation flux is broken, and the high-flux and high interception performance of the small-molecular pollutants are realized.
The existing conductive films mainly have two main types: an organic polymer conductive film and an inorganic conductive film. The preparation of the organic polymer conductive film mainly comprises three methods of using conductive polymer materials, adding conductive materials into the materials and preparing conductive functional layers on the surfaces, wherein the polymer conductive film prepared by the method is generally larger in limiting resistance, fewer in electrocatalytic sites and easy to fall off and damage due to natural insulation of the polymer. The inorganic conductive film mainly comprises three kinds of metal film, carbon film and conductive ceramic film. The metal film, the carbon film and the conductive ceramic film of the traditional process are usually prepared by an extrusion molding mode, so that the film structure is difficult to regulate and control, the mechanical property is poor, the metal film and the carbon film are easy to be corroded by electrochemistry when being used as an electrochemical anode, and the stability is poor.
Disclosure of Invention
In order to solve the problems, the invention provides a carbonized ceramic conductive film and a preparation method thereof, and the method can adjust the film structure and the film hole size, and simultaneously remarkably reduce the resistance of the film and ensure that the film has good mechanical property and stability.
The preparation method of the carbonized ceramic membrane conductive film comprises the following steps:
s1, dissolving a polymer material into a solvent, adding ceramic particles after complete dissolution, and uniformly stirring to obtain a casting solution;
s2, pouring the casting solution on a clean glass plate for film scraping after standing and defoaming, and immediately immersing the glass plate with the casting solution in a coagulating bath after film scraping is completed until the glass plate is completely phase-converted;
s3, taking the film with complete phase inversion out of the coagulating bath, freezing and then carrying out vacuum drying;
s4, cutting the dried membrane, clamping the membrane in the membrane by using two layers of ceramic plates for pre-oxidation, carbonizing at high temperature after the pre-oxidation is finished, and naturally cooling to room temperature after the carbonization is finished to obtain the carbonized ceramic conductive film.
Further, the polymer material is one or more of polypropylene, polysulfone, polyacrylonitrile, polyimide and polyvinylidene fluoride.
Preferably, the polymeric material is polyacrylonitrile.
Further, the solvent is one or more of DMAc, DMF, NMP, DMSO.
Preferably, the solvent is DMF.
Further, the ceramic particles are one or more of alumina, silica, zirconia, silicon carbide and kaolin.
Preferably, the ceramic particles are alumina.
Further, the polymer material content in the casting solution is 5-20wt%, the ceramic particle content is 30-50wt%, and the rest is solvent.
Preferably, the polymer material content in the casting solution is 6.25wt%, the ceramic particle content is 37.5wt%, and the remainder is solvent.
Further, the coagulating bath is a pure water coagulating bath, an ethanol coagulating bath or a mixed coagulating bath with the mass ratio of ethanol to water being 3:7.
Preferably, when the pore structure of the carbonized ceramic conductive film is a finger-shaped pore, the coagulation bath is a pure water coagulation bath.
Preferably, when the pore structure of the carbonized ceramic conductive film is a sponge-like pore, the coagulation bath is an ethanol coagulation bath.
Further, the thickness of the film after film scraping is 300-1000 μm.
Preferably, the thickness of the film after scraping is 550 μm.
Further, the pre-oxidation is carried out in an air atmosphere, the heating rate is 2 ℃/min, the pre-oxidation temperature is 100 ℃ to 300 ℃, and the heat preservation time is 150min.
Preferably, the pre-oxidation temperature is 230 ℃.
Further, the high-temperature carbonization is performed in a nitrogen atmosphere, the heating rate is 3 ℃/min, the high-temperature carbonization temperature is 800-1600 ℃, and the heat preservation time is 60min.
Preferably, the high temperature carbonization temperature is 1200 ℃.
The invention also provides a carbonized ceramic conductive film prepared by the method.
According to the invention, a phase inversion technology is adopted to firstly dissolve polyacrylonitrile and perform mixed phase inversion on ceramic particles to prepare a polyacrylonitrile polymer ceramic film precursor, and then high-temperature carbonization is performed after low-temperature pre-oxidation to convert the polyacrylonitrile polymer in the ceramic film precursor into a graphite carbon structure with high conductivity, so that the preparation of the carbonized ceramic conductive film is realized, and the carbonized ceramic film has high conductivity (resistance is less than 20 omega) and high electrocatalytic performance.
The invention controls the pore size and the structure of the carbonized ceramic membrane by adjusting the phase inversion process parameters. When pure water is used as a coagulating bath, the solvent and water exchange rate is high, instantaneous phase separation occurs on the surface of the membrane in the phase inversion process, and the deposition speed difference exists between the inside and the surface of the membrane, so that the membrane structure presents an asymmetric membrane structure with compact surface layer and finger-shaped macropores inside. When ethanol is used as a coagulating bath, the exchange rate of the solvent and the ethanol is relatively slow, phase separation can be delayed in the phase inversion process, and the deposition rate of polymer phases on the surface of the membrane and the inside of the membrane is relatively small, so that the membrane structure presents a spongy pore structure similar to the surface layer and the inside. As the viscosity of the casting solution increases with the increase of the addition amount of the polymer material, the film formed by phase inversion is more compact; the carbonized ceramic membrane is more compact due to more graphite carbon generated by carbonization. The pore diameter of the membrane pores is 180-400nm, the porosity is 65% -80%, and the membrane structure is regulated and controlled between the spongy pores and the finger-shaped pores by regulating and controlling the selection of the phase inversion coagulation bath and the addition amount of the polymer material.
Compared with the prior art, the invention has the beneficial technical effects that:
the carbonized ceramic membrane conductive film is coupled with an external power supply, so that the carbonized ceramic membrane conductive film has high permeation flux and good removal performance on small molecular pollutants. Meanwhile, the carbonized ceramic membrane prepared by the invention has adjustable membrane structure, membrane pore size, low resistance, good mechanical property and stability.
Drawings
The invention is further described with reference to the following description of the drawings.
FIG. 1 is an SEM image of the surface morphology of a carbonized ceramic conductive film of examples 1-6 of the present invention;
FIG. 2 is a SEM image of the cross-sectional morphology of a carbonized ceramic conductive film of examples 1-6 of the present invention;
FIG. 3 is a graph showing the resistance of a carbonized ceramic conductive film of examples 1-6 of the present invention;
in the figure, the number M is the addition of polyacrylonitrile, H is pure water phase conversion, and E is ethanol phase conversion.
Detailed Description
The technical scheme provided by the invention is further described below by combining with the embodiment.
The preparation methods of examples 1-6 are as follows:
dissolving polyacrylonitrile in DMF in a ball milling tank, adding alumina particles after complete dissolution, putting a proper amount of grinding balls into a ball mill, and ball milling and stirring at 300r/min for 48 hours to ensure uniform mixing of casting solution;
taking out the ball milling tank after completely and uniformly stirring, putting the ball milling tank into an ultrasonic machine for ultrasonic treatment for 30min, and standing for more than 4h to ensure complete defoaming;
pouring the defoamed casting solution on a clean and flat glass plate, regulating the thickness of the glass plate to 550 mu m by using a scraper, and then placing the glass plate into pure water or ethanol coagulation bath for 24 hours to ensure complete phase inversion;
taking out the film after phase conversion, putting the film into a refrigerator for complete freezing, and putting the film into a freeze dryer for drying;
and after the drying is finished, taking out the membrane, cutting the membrane into a membrane with the diameter of 28mm, clamping the membrane in the middle by using two ceramic plates, putting the membrane into a tube furnace, heating to 230 ℃ at the heating rate of 2 ℃/min under the air atmosphere, preserving heat for 150min, and naturally cooling to room temperature. And then heating to 1200 ℃ in a tube furnace at a heating rate of 3 ℃/min under nitrogen atmosphere control, preserving heat for 60min, and naturally cooling to room temperature to obtain the carbonized ceramic conductive film.
As can be seen from the figures 1 and 2, the invention can control the membrane pore size and the membrane structure by the addition of polyacrylonitrile and the selection of a coagulating bath, and the prepared carbonized ceramic membrane has higher conductive performance and lower resistance, and the resistance of the carbonized ceramic membrane is less than 20Ω when the carbonization temperature reaches 1200 ℃.
Test example 1
The dye retention properties of the conductive films of examples 1 to 6 were tested with Congo Red (CR), rhodamine b (Rhb), methyl Blue (MB), methyl Orange (MO) dye solutions having a dye concentration of 20mg/L and a sodium sulfate concentration of 7.2g/L, the films were used as a filter unit under an applied voltage of 1.5V while the dye solutions were filtered off as anodes, and the absorbance of the CR, rhb, MB, MO dye solutions and the filtrate at wavelengths 498nm, 554nm, 592nm, 464nm was measured using an ultraviolet spectrophotometer, and the dye retention rates were calculated as follows:
| sample naming | Pure water flux | Average removal rate of four dyes |
| Example 1 | 14133LMH/bar | 97.6％ |
| Example 2 | 8213LMH/bar | 99.5％ |
| Example 3 | 6404LMH/bar | 99.5％ |
| Example 4 | 2577.5LMH/bar | 99.5％ |
| Example 5 | 1610LMH/bar | 99.8％ |
| Example 6 | 977LMH/bar | 99.8％ |
Comparative example 1
A method for preparing an organic polymer conductive film, which comprises the following steps:
mixing carbon nanotubes with the mass ratio of 1:1 with polyvinylidene fluoride co-hexafluoropropylene, adding nano zeolite accounting for 60% of the mass of the carbon nanotubes, and dispersing the nano zeolite into a solvent with the volume ratio of water to ethanol of 1:1 by using an ultrasonic machine for 10min; the resulting dispersion was then vacuum filtered onto filter paper and treated at 160 ℃ for 1h to incorporate polyvinylidene fluoride co-hexafluoropropylene within the nano zeolite and carbon nanotube structure, after which the membrane was removed and tested as follows:
the membrane has a pore diameter of 50nm, a resistance of 200 omega, a porosity of 40%, a pure water flux of 210LMH/bar and a dye removal rate of 60% at 1.5V.
Comparative example 2
A preparation method of an organic polymer ceramic composite conductive film comprises the following steps:
the ceramic support layer was immersed in a reduced graphene oxide (5 wt%), polypyrrole (30 wt%) and ethanol solution (65 wt%) at 40 ℃ for 30min, then heated at 110 ℃ for 4 hours to enhance the binding force between the ceramic support and the reduced graphene oxide, and then the membrane was removed for testing, with the following results:
the membrane aperture is 300nm, the resistance is 1KΩ, the porosity is 50%, the pure water flux is 3523LMH/bar, and the 1.5V dye removal rate is 12%.
Comparative example 3
Preparation method of organic polymer conductive film
First, 0.36g zinc acetate and 0.24g urea were dissolved with a mixture of 160mL deionized water and 24mL ethanolamine. And (3) carrying out ultrasonic dispersion on the solution for 1h to obtain a uniform solution. Then 0.04g of reduced graphene oxide (rGO) is added into the solution and dispersed by ultrasonic. The solution was heated in a hydrothermal kettle at 120℃for 12h. And (3) centrifugally washing the collected gray precipitate, and finally drying at 60 ℃ to obtain rGO-ZnO.
Polysulfone, polyvinylpyrrolidone 1% by mass and rGO-ZnO 1.5% by mass of the polysulfone addition were added to DMAc (83%), and after ultrasonic dispersion at 60W for 30min, stirred at 60 ℃ to a homogeneous casting solution, scraped and phase-inverted in a pure water coagulation bath on a clean glass plate, after which the membrane was removed and tested as follows:
the membrane pore diameter is 78nm, the resistance is 405 omega, the porosity is 60%, the pure water flux is 283LMH/bar, and the dye retention rate is 40% at 1.5V.
Comparative example 4
Preparation method of carbon conductive film
Coal was ground into fine particles (4 μm) and then mixed with a polyvinyl alcohol binder (5 wt%), pressed into a membrane with a diameter of 30mm under a pressure of 3Mpa by a hydraulic press, dried in an air atmosphere, carbonized in argon at 900 ℃ for 1h, and the final product was naturally cooled to room temperature for testing, with the following results:
the membrane has a pore diameter of 500nm, a resistance of 18 omega, a porosity of 43.8%, a pure water flux of 632LMH/bar and a dye retention of 70% at 1.5V.
Test example 2
The dye retention performance of the conductive films of comparative examples 5 to 8 was tested with Congo Red (CR), rhodamine b (Rhb), methyl Blue (MB), methyl Orange (MO) dye solutions, the dye concentration in the dye solutions was 20mg/L, sodium sulfate was 7.2g/L, the dye solutions were prepared, and the films were filtered out as a filter unit and simultaneously as anodes under an applied voltage of 1.5V, and the fuel retention rate was calculated as follows:
the principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to assist in understanding the methods of the present invention and the core ideas thereof; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the invention.
Claims (10)
1. The preparation method of the carbonized ceramic conductive film is characterized by comprising the following steps of:
s1, dissolving a polymer material into a solvent, adding ceramic particles after complete dissolution, and uniformly stirring to obtain a casting solution;
s2, pouring the casting solution on a clean glass plate for film scraping after standing and defoaming, and immediately immersing the glass plate with the casting solution in a coagulating bath after film scraping is completed until the glass plate is completely phase-converted;
s3, taking the film with complete phase inversion out of the coagulating bath, freezing and then carrying out vacuum drying;
s4, cutting the dried membrane, clamping the membrane in the membrane by using two layers of ceramic plates for pre-oxidation, carbonizing at high temperature after the pre-oxidation is finished, and naturally cooling to room temperature after the carbonization is finished to obtain the carbonized ceramic conductive film.
2. The method for preparing a carbonized ceramic conductive film according to claim 1, wherein the polymer material is one or more of polypropylene, polysulfone, polyacrylonitrile, polyimide, and polyvinylidene fluoride.
3. The method for producing a carbonized ceramic conductive film according to claim 1, wherein the solvent is one or more of dimethylacetamide (DMAc), dimethylformamide (DMF), N-methylpyrrolidone (NMP), and Dimethylsulfoxide (DMSO).
4. The method for producing a carbonized ceramic conductive film according to claim 1, wherein the ceramic particles are one or more of alumina, silica, zirconia, silicon carbide, and kaolin.
5. The method for producing a carbonized ceramic conductive film according to claim 1, wherein the polymer material content in the casting solution is 5wt% to 20wt%, the ceramic particle content is 30wt% to 50wt%, and the remainder is a solvent.
6. The method for producing a carbonized ceramic conductive film according to claim 1, wherein the coagulation bath is a water coagulation bath, an ethanol coagulation bath, or a solvent/water mixed coagulation bath.
7. The method for producing a carbonized ceramic conductive film as described in claim 1, wherein the thickness of the film after the film scraping is 300 to 1000 μm.
8. The method for preparing a carbonized ceramic conductive film according to claim 1, wherein the pre-oxidation is performed in an air atmosphere at a heating rate of 2 ℃/min, a pre-oxidation temperature of 100 ℃ to 300 ℃ and a holding time of 150min.
9. The method for preparing a carbonized ceramic conductive film according to claim 1, wherein the high-temperature carbonization is performed under nitrogen atmosphere, the heating rate is 3 ℃/min, the high-temperature carbonization temperature is 800 ℃ to 1600 ℃, and the heat preservation time is 60min.
10. A carbonized ceramic conductive film prepared by the method of any one of claims 1-9.
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