CN114432908B - Composite conductive film and preparation method and application thereof - Google Patents
Composite conductive film and preparation method and application thereof Download PDFInfo
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- CN114432908B CN114432908B CN202210220088.2A CN202210220088A CN114432908B CN 114432908 B CN114432908 B CN 114432908B CN 202210220088 A CN202210220088 A CN 202210220088A CN 114432908 B CN114432908 B CN 114432908B
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a composite conductive film and a preparation method and application thereof. The invention provides a composite conductive film, which comprises a conductive film bottom layer and a conductive film surface layer which are sequentially stacked; the conductive film bottom layer comprises a first conductive compound and zirconia; the conductive film facing layer comprises a second conductive compound and copper oxide; the first and second electrically conductive composites comprise an electrically conductive polymer, antimony doped tin dioxide, and graphite. The composite conductive film provided by the invention has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of sewage treatment membranes, and particularly relates to a composite conductive membrane and a preparation method and application thereof.
Background
A large amount of raw material reagents are required to be added in the production processes of leaching, precipitation and the like of rare earth products, a large amount of wastewater containing ammonia nitrogen and organic matters is generated in the production process, and the surrounding ecological environment is seriously polluted. The conventional treatment process comprises a multi-effect ammonia evaporation method, a struvite precipitation method or an ion exchange method, has the problems of low treatment efficiency, serious secondary pollution, overhigh equipment investment cost and the like, and is difficult to reach higher effluent standard. The membrane separation process based on the ceramic inorganic membrane has a good treatment effect in practice, but the membrane pollution phenomenon is serious in the large-scale application process, and the treatment effect is influenced.
The electrochemical composite membrane separation technology introduces electrochemistry on the basis of membrane separation, so that pollutants in water can be degraded, the phenomenon of concentration polarization on the surface of the membrane can be effectively relieved under the action of an electric field, and the service life of the membrane is prolonged; the conductive ceramic membrane is obtained by combining the conductive substance with the ceramic membrane, so that the problem of membrane pollution can be further relieved. Chinese patent publication No. CN102671551A discloses a conductive ceramic membrane, which is prepared by blending a matrix polymer with a conductive polymer, carbon powder or carbon paper, blending a casting solution with powder, or compounding the casting solution with carbon paper to form a membrane, so as to further improve the effect of sewage treatment, but the obtained ceramic membrane has poor conductivity.
Disclosure of Invention
The invention aims to provide a composite conductive film which has excellent conductive performance.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a composite conductive film, which comprises a conductive film bottom layer and a conductive film surface layer which are sequentially stacked;
the conductive film bottom layer comprises a first conductive compound and zirconia;
the conductive film facing layer comprises a second conductive compound and copper oxide;
the first and second conductive composites include a conductive polymer, antimony doped tin dioxide, and graphite.
Preferably, the mass ratio of the conductive polymer, the antimony-doped tin dioxide and the graphite in the first conductive composite is (80-100): (15-30): (0.5-1);
the mass ratio of the conductive polymer, the antimony-doped tin dioxide and the graphite in the second conductive composite is (80-100): (30-35): (0.4-0.6).
Preferably, the conductive polymer comprises one or more of polypyrrole, polyacetylene, polythiophene and polyaniline.
Preferably, the mass ratio of the first conductive compound to the zirconia is 8 to 12:1;
the mass ratio of the second conductive compound to the copper oxide is 15-20: 1.
preferably, the thickness of the conductive film bottom layer is 200 to 400 μm;
the thickness of the conductive film surface layer is 50-100 mu m.
The invention also provides a preparation method of the composite conductive film, which comprises the following steps:
first mixing a first conductive compound, zirconia and a first dispersing agent to obtain first slurry;
secondly, mixing a second conductive compound, copper oxide and a second dispersing agent to obtain second slurry;
coating the first slurry on the surface of a substrate, and then carrying out first calcination to obtain a bottom layer of the conductive film;
and coating a second slurry on the bottom surface of the conductive film, and then carrying out second calcination to obtain the composite conductive film.
Preferably, the first dispersant and the second dispersant each comprise terpineol, ethyl cellulose, and castor oil;
the mass ratio of the terpineol, the ethyl cellulose and the castor oil in the first dispersant and the second dispersant is (20-30): 1: (3-5).
Preferably, the mass ratio of the first conductive compound to the first dispersant is 1:2 to 3;
the mass ratio of the second conductive compound to the second dispersant is 1:3 to 5.
Preferably, the temperature of the first calcination is 700-800 ℃, and the time is 100-120 min;
the temperature of the second calcination is 800-900 ℃, and the time is 150-200 min.
The invention also provides the application of the composite conductive film in the technical scheme or the composite conductive film prepared by the preparation method in the claim in sewage treatment.
The invention provides a composite conductive film, which comprises a conductive film bottom layer and a conductive film surface layer which are sequentially stacked; the conductive film bottom layer comprises a first conductive compound and zirconia; the conductive film facing layer comprises a second conductive compound and copper oxide; the first and second electrically conductive composites comprise an electrically conductive polymer, antimony doped tin dioxide, and graphite. According to the invention, the conductive polymer and antimony-doped tin dioxide are used as conductive fillers, and the dispersibility of the conductive fillers can be improved by adding graphite, so that agglomeration is prevented; the copper oxide is combined with the zirconium oxide on the basis of preventing the conductive composite film from cracking, so that the combination stability of the matrix and the conductive film is further balanced, and the composite conductive film provided by the invention has excellent conductivity under the synergistic action of all components.
Drawings
FIG. 1 shows α -Al in example 1 2 O 3 Testing the surface roughness of the ceramic membrane;
FIG. 2 shows the results of the surface roughness test of the composite conductive film obtained in example 1;
fig. 3 is a cyclic voltammetry test chart of the composite conductive film obtained in example 1.
Detailed Description
The invention provides a composite conductive film, which comprises a conductive film bottom layer and a conductive film surface layer which are sequentially stacked;
the conductive film bottom layer comprises a first conductive compound and zirconia;
the conductive film facing layer comprises a second conductive compound and copper oxide;
the first and second conductive composites include a conductive polymer, antimony doped tin dioxide, and graphite.
In the invention, the conductive polymer preferably comprises one or more of polypyrrole, polyacetylene, polythiophene and polyaniline; when the conductive polymer is two or more selected from the above specific choices, the present invention does not specifically limit the proportion of the specific substance, and the conductive polymer may be mixed in any proportion.
In the present invention, the particle size of the zirconia is preferably 10 to 30nm, more preferably 12 to 28nm, and still more preferably 15 to 25nm.
In the invention, the antimony doped tin dioxide is preferably commercially available antimony doped tin dioxide or self-made antimony doped tin dioxide. In the invention, the molar ratio of tin to antimony in the antimony-doped tin dioxide is preferably 8.5-10: 1, more preferably 8.6 to 9.8:1, more preferably 9.0 to 9.5:1.
in the present invention, when the antimony-doped tin dioxide is preferably a self-made antimony-doped tin dioxide, the preparation method of the antimony-doped tin dioxide preferably comprises the following steps:
SnCl 2 、SbCl 3 And mixing the antimony-doped tin dioxide with ethanol, adding ammonia water for alkalization reaction, and calcining to obtain the antimony-doped tin dioxide.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the SnCl 2 And SbCl 3 Preferably 8.5 to 10:1, more preferably 8.6 to 9.8:1, more preferably 9.0 to 9.5:1.
in the present invention, the mass concentration of ethanol is preferably 95%. In the invention, snCl is contained in the mixed solution obtained by mixing 2 The molar concentration of (B) is preferably 0.2 to 0.5mol/L, more preferably 0.3 to 0.4mol/L.
In the present invention, the mixing is preferably performed under stirring. The stirring condition parameters are not specially limited, and the stirring can be carried out uniformly.
In the present invention, the mass concentration of the ammonia water is preferably 24%. The amount of the ammonia water added is not particularly limited, and the pH value of the mixed solution can be adjusted to 10.
In the present invention, the temperature of the alkalization reaction is preferably 50 to 70 ℃, more preferably 55 to 65 ℃, and still more preferably 60 ℃; the time is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours, and still more preferably 4 hours. .
After the alkalization reaction is finished, the invention also preferably comprises the step of carrying out post-treatment on the obtained product; the post-treatment preferably comprises cooling, separation, washing and drying in sequence.
The cooling and separation process of the present invention is not particularly limited, and a process known to those skilled in the art may be used. In the invention, the washing reagent used for washing is preferably deionized water; the number of washing is preferably 3. The present invention does not require a particular washing process, and can be performed as is well known to those skilled in the art. The drying process is not particularly limited in the present invention, and those skilled in the art can use the drying process.
In the present invention, the temperature of the calcination is preferably 600 to 700 ℃, more preferably 620 to 680 ℃, and more preferably 630 to 650 ℃; the time is preferably 20 to 30min, more preferably 22 to 28min, and still more preferably 23 to 25min. In the present invention, the rate of temperature increase to the calcination temperature is preferably 2 to 3 ℃/min. In the present invention, the calcination is preferably carried out in a muffle furnace.
In the invention, the self-made antimony-doped tin dioxide is applied to the composite conductive film, and compared with the commercially available antimony-doped tin dioxide, the obtained composite conductive film has better conductivity.
In the present invention, the mass ratio of the first conductive compound to zirconia is preferably 8 to 12:1, more preferably 9 to 11:1, more preferably 10:1. in the present invention, the mass ratio of the conductive polymer, antimony-doped tin dioxide, and graphite in the first conductive composite is preferably (80 to 100): (15-30): (0.5 to 1), more preferably (85 to 95): (18 to 28): (0.6 to 0.9), more preferably (88 to 92): (20-25): (0.7-0.8).
In the present invention, the mass ratio of the second conductive compound to the copper oxide is preferably 15 to 20:1, more preferably 16 to 19:1, more preferably 17 to 18:1. in the present invention, the mass ratio of the conductive polymer, the antimony-doped tin dioxide, and the graphite in the second conductive composite is preferably (80 to 100): (30-35): (0.4 to 0.6), more preferably (85 to 95): (31-34): (0.4 to 0.5), more preferably (88 to 92): (32-33): (0.4-0.5).
In the present invention, the thickness of the conductive film underlayer is preferably 200 to 400 μm, more preferably 250 to 380 μm, and still more preferably 300 to 350 μm. In the present invention, the thickness of the conductive film surface layer is preferably 50 to 100 μm, more preferably 60 to 90 μm, and still more preferably 70 to 80 μm.
The invention also provides a preparation method of the composite conductive film, which comprises the following steps:
first mixing a first conductive compound, zirconia and a first dispersing agent to obtain first slurry;
secondly, mixing a second conductive compound, copper oxide and a second dispersing agent to obtain second slurry;
coating the first slurry on the surface of a substrate, and then carrying out first calcination to obtain a bottom layer of the conductive film;
and coating a second slurry on the surface of the bottom layer of the conductive film, and then carrying out second calcination to obtain the composite conductive film.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, a first conductive compound, zirconium oxide and a first dispersing agent are subjected to first mixing to obtain a first slurry.
In the present invention, the first dispersant preferably includes terpineol, ethylcellulose, and castor oil; the mass ratio of the terpineol to the ethyl cellulose to the castor oil is preferably (20-30): 1: (3-5), more preferably (22-28): 1: (3 to 4), more preferably (24 to 26): 1: (3-4).
In the present invention, the first dispersant is preferably obtained by preparation; the preparation method preferably comprises the following steps: and mixing terpineol, ethyl cellulose and castor oil, stirring for 30min at normal temperature, and then stirring for 3h at 90 ℃ to obtain the first dispersing agent. The mixing process and the stirring parameters are not particularly limited in the present invention, and those well known to those skilled in the art can be used.
In the invention, the first dispersing agent can generate chelation with the conductive polymer and the antimony-doped tin dioxide, so that the conductivity of the composite conductive film is further improved.
In the present invention, the first conductive polymer is preferably obtained by a production method, which preferably includes the steps of: and mixing the conductive polymer, the antimony-doped tin dioxide and the graphite to obtain the first conductive polymer.
The mixing process is not particularly limited in the present invention, and may be performed as is well known to those skilled in the art. In the present invention, the mass ratio of the conductive polymer, antimony-doped tin dioxide, and graphite in the first conductive composite is preferably (80 to 100): (15-30): (0.5 to 1), more preferably (85 to 95): (18 to 28): (0.6 to 0.9), more preferably (88 to 92): (20-25): (0.7-0.8). In the present invention, the mass ratio of the first conductive compound to zirconia is preferably 8 to 12:1, more preferably 9 to 11:1, more preferably 10:1. in the present invention, the mass ratio of the first conductive compound to the first dispersant is preferably 1:2 to 3, more preferably 1:2.2 to 2.8, more preferably 1:2.4 to 2.6.
In the present invention, the first mixing process is preferably ball milling. In the invention, the grinding bodies used for ball milling are preferably steel forgings with the diameter of 18 mm multiplied by 22 mm. In the invention, the ball-to-material ratio in the ball milling process is preferably 5-7: 1 is more preferably 6:1. in the present invention, the process of ball milling is preferably as follows: ball milling is carried out for 20min, then cooling is carried out for 40min, and the operation is recorded as a cycle, and the cycle is repeated for 4-5 times. In the present invention, the ball milling is preferably performed in a ball mill.
In the invention, the zirconia can adjust the thermal expansion coefficient between the bottom layer of the conductive film and the substrate, can balance the binding force between the substrate and the conductive polymer, and further improves the binding stability of the bottom layer of the conductive film and the substrate.
In the invention, the graphite can further improve the dispersibility of each component in the slurry; and the subsequent calcination process can play a role of pore forming, so that the permeability of the surface of the conductive film layer is increased, and the pore structure on the surface of the film is prevented from being completely blocked.
According to the invention, a second slurry is obtained by second mixing of a second conductive compound, copper oxide and a second dispersant.
In the present invention, the second dispersant is the same as the first dispersant, and thus, the description thereof is omitted. In the present invention, the second conductive compound is preferably prepared by the same method as the first conductive compound, and thus, the description thereof is omitted.
In the present invention, the mass ratio of the conductive polymer, antimony-doped tin dioxide, and graphite in the second conductive composite is preferably (80 to 100): (30-35): (0.4 to 0.6), more preferably (85 to 95): (31-34): (0.4 to 0.5), more preferably (88 to 92): (32-33): (0.4-0.5). In the present invention, the mass ratio of the second conductive compound to the copper oxide is preferably 15 to 20:1, more preferably 16 to 19:1, more preferably 17 to 18:1. in the present invention, the mass ratio of the second conductive compound to the second dispersant is preferably 1:3 to 5, more preferably 1:4.
in the present invention, the process of the second mixing is preferably ball milling. In the present invention, the grinding body used for ball milling is preferably steel forging with a diameter of 15X 20 mm. In the present invention, the ball-to-material ratio in the ball milling process is preferably 5 to 7. In the present invention, the process of ball milling is preferably as follows: ball milling is carried out for 20min, cooling is carried out for 40min, and the circulation is recorded as one cycle, and is repeated for 4-5 times. In the present invention, the ball milling is preferably performed in a ball mill.
In the invention, the copper oxide can further promote the sintering of the conductive film surface layer, prevent the conductive composite film from cracking and further improve the stability and the conductivity of the composite conductive film.
After the first slurry is obtained, the surface of a substrate is coated with the first slurry, and then first calcination is carried out to obtain a bottom layer of the conductive film.
In the present invention, the matrix preferably comprises α-Al 2 O 3 Ceramic, siC ceramic or ZrO films 2 A ceramic membrane.
Before the coating, the invention also preferably comprises the steps of pretreating the substrate; the pretreatment preferably comprises impurity removal, cleaning and drying which are sequentially carried out.
In the invention, the impurity removal process is preferably as follows: and sequentially soaking the carrier in ethanol and sodium hydroxide solution to remove impurities.
In the present invention, the mass concentration of ethanol is preferably > 99%. In the present invention, the molar concentration of the sodium hydroxide solution is preferably 0.15mol/L. The process of soaking is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
In the present invention, the cleaning is preferably performed using ultrapure water. The present invention does not require special procedures for the washing and drying, and can be performed as is well known to those skilled in the art.
In the present invention, the coating is preferably performed by dip-coating. In the present invention, the dipping and pulling process is preferably as follows: and (3) carrying out dip-drawing on the matrix in the first slurry, carrying out drying treatment after each dip-drawing is carried out for 2-5 times, and repeating the above processes for 3-10 times. In the present invention, the speed of the dipping and pulling is preferably 0.5cm/s. In the present invention, the temperature of the drying treatment is preferably 70 ℃; the time is preferably 20min. In the present invention, the drying treatment is preferably performed in a forced air drying oven.
In the present invention, the temperature of the first calcination is preferably 700 to 800 ℃, more preferably 720 to 780 ℃, and still more preferably 740 to 750 ℃; the time is preferably 100 to 120min, more preferably 105 to 115min, and still more preferably 110min. In the present invention, the rate of temperature increase to the temperature for the first calcination is preferably 3 to 5 ℃/min, and more preferably 4 ℃/min. In the present invention, the atmosphere of the first calcination is preferably nitrogen. In the present invention, the first calcination is preferably carried out in a muffle furnace.
After the first calcination is completed, the present invention preferably further includes cooling the obtained bottom layer of the conductive film. The present invention does not require any special procedure for the cooling treatment, and can be performed as is well known to those skilled in the art. In the present invention, the temperature after the cooling treatment is preferably room temperature.
After the second slurry and the bottom layer of the conductive film are obtained, the second slurry is coated on the bottom layer of the conductive film, and then second calcination is carried out to obtain the composite conductive film.
In the present invention, the coating is preferably performed by spraying. In the present invention, the spraying process is preferably as follows: placing a substrate containing a bottom layer of the conductive film on an electric furnace, heating to 400-450 ℃, and monitoring the surface temperature in real time by using an infrared thermometer in the heating process; and then spraying the second slurry on the surface of the bottom layer of the conductive film. In the present invention, the amount of the spray is preferably 1 to 3mL/cm 2 More preferably 1.2 to 2.8mL/cm 2 More preferably 1.5 to 2.5mL/cm 2 。
In the invention, the temperature of the second calcination is preferably 800-900 ℃, more preferably 820-880 ℃, and more preferably 830-850 ℃; the time is preferably 150 to 200min, more preferably 160 to 190min, and still more preferably 170 to 180min. In the present invention, the rate of temperature increase to the temperature of the second calcination is preferably 3 to 5 ℃/min, and more preferably 4 ℃/min. In the present invention, the atmosphere of the second calcination is preferably air. In the present invention, the second calcination is preferably carried out in a muffle furnace.
The invention also provides the application of the composite conductive film or the composite conductive film prepared by the preparation method in the technical scheme in sewage treatment. The present invention is not particularly limited to the specific embodiments for the applications, and those skilled in the art will be familiar with the application.
In order to further illustrate the present invention, the following detailed description of the composite conductive film provided by the present invention, the preparation method and the application thereof are made with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
alpha-Al is added 2 O 3 Sequentially soaking the ceramic membrane in ethanol (the ethanol concentration is 99%) and a sodium hydroxide solution (the molar concentration is 0.15 mol/L), then cleaning by adopting ultrapure water, and drying for later use;
90g of SnCl are taken 2 、10g SbCl 3 Mixing with 100mL of ethanol (the concentration is 95%), adding ammonia water to adjust the pH value to 10, carrying out an alkalization reaction for 4 hours at 70 ℃, cooling to room temperature after the reaction is finished, then adding water to filter for 3 times, drying the obtained solid, placing the dried solid in a muffle furnace, heating to 700 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation for 150min to obtain antimony-doped tin dioxide;
mixing 600g of terpineol, 20g of ethyl cellulose and 60g of castor oil, stirring for 30min at normal temperature, and then stirring for 3h at 90 ℃ to obtain a dispersing agent;
putting 80g of polypyrrole, 15g of antimony-doped tin dioxide, 0.5g of graphite, 10g of zirconia and 220g of dispersing agent into a ball mill for ball milling, wherein a milling body adopted in the ball milling process is a phi 18 multiplied by 22mm steel forging, and the ball-to-material ratio is 6:1, performing ball milling for 20min, cooling for 40min, and repeating for 3 times to obtain first slurry;
putting 80g of polypyrrole, 30g of antimony-doped tin dioxide, 0.5g of graphite, 6g of copper oxide and 350g of dispersing agent into a ball mill for ball milling, wherein a milling body adopted in the ball milling process is a phi 15 multiplied by 20mm steel forging, and the ball-to-material ratio is 5:1, performing ball milling for 20min each time, cooling for 40min, and repeating for 5 times to obtain second slurry;
dipping and pulling the pretreated substrate in the first slurry, drying the substrate in a forced air drying oven at 70 ℃ for 20min after each dipping and pulling for 3 times, repeating the above process for 5 times, placing the substrate in a muffle furnace, heating to 800 ℃ at the speed of 5 ℃/min, calcining for 120min, and cooling to room temperature to obtain a bottom layer of the conductive film;
heating the substrate containing the bottom layer of the conductive film on an electric furnace to a surface temperature of 420 ℃, monitoring the surface temperature in real time by using an infrared thermometer, and spraying the second slurry on the surface of the bottom layer of the conductive film, wherein the spraying amount is 1.2mL/cm 2 After the spraying is finished, the mixture is placed in a muffle furnace to be heated to 800 ℃ at the speed of 4 ℃/min and calcined for 150miAnd n, obtaining the composite conductive layer.
Application example 1
The composite conductive film obtained by the invention is used as a cathode, a stainless steel electrode is used as an anode, and the rare earth ore wastewater (COD concentration is 420ppm, ammonia nitrogen concentration is 84 ppm) is treated under the following test conditions: the current density is 18mA/cm 2 The distance between polar plates is 2.5cm, the membrane suction pressure is-0.08 MPa, and the test result is as follows: through the treatment of the composite conductive film provided by the invention, the COD concentration of the obtained effluent is 68ppm, and the ammonia nitrogen concentration is 23ppm. When the membrane flux is attenuated to 30% of the initial flux, the treatment time of the composite conductive membrane provided by the invention is 40h, while the treatment time of the conventional ceramic membrane is 18h, which shows that the conductive composite membrane provided by the invention has higher sewage treatment efficiency.
Performance testing
Test example 1
Composite conductive film obtained in example 1 and α -Al used therefor 2 O 3 The ceramic membrane is subjected to a surface roughness test, and the test results are shown in fig. 1 and fig. 2, wherein fig. 1 shows alpha-Al 2 O 3 The surface roughness test results of the ceramic films can be seen from fig. 1: alpha-Al 2 O 3 The surface roughness of the ceramic membrane is high, the height difference between peaks and valleys is 571.5nm at most, and the average roughness Ra of the membrane surface is 421nm; fig. 2 is a result of testing the surface roughness of the composite conductive film provided by the present invention, and it can be seen from fig. 2 that the surface roughness of the composite conductive film provided by the present invention is reduced, peaks of the film surface are relatively arranged in a coherent manner, gaps between the peaks and valleys are uniformly distributed, a height difference between the peaks and valleys is 270.7nm at most, and the roughness Ra of the film surface is as low as 212nm.
Test example 2
The sheet resistance of the composite conductive film obtained in example 1 was measured by a four-probe method, and different areas of the film surface were measured 6 times at 10 ℃, 20 ℃ and 30 ℃ respectively, and the results are shown in table 1.
Table 1 test results of sheet resistance of composite conductive film obtained in example 1
As can be seen from table 1: under the condition of normal temperature of 10-30 ℃, the mean value of the square resistance of the composite conductive film obtained by the invention is 40.2-42.7 omega/sq, the result of measuring the square resistance of the inner film surface in different areas in one time is smooth, and the standard deviation is less than 1.6, which shows that the conductive coating is uniformly distributed and has excellent conductivity.
Test example 3
The cyclic voltammetry of the composite conductive film obtained in example 1 was measured by a potentiostatic test method, the test step size was 2.44 mV/step, the scan rate was 20mV/s to 80mV/s, and the test results are shown in FIG. 3. It can be seen from FIG. 3 that the composite conductive film obtained in the present invention has an oxygen evolution potential of about 0.7296V (vs Ag/AgCl) and a hydrogen evolution potential of about-0.5893V (vs Ag/AgCl), and has excellent electrocatalytic capacity.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A composite conductive film is characterized by comprising a base body, a conductive film bottom layer and a conductive film surface layer, wherein the conductive film bottom layer and the conductive film surface layer are sequentially stacked on the surface of the base body;
the matrix comprises alpha-Al 2 O 3 Ceramic membranes, siC ceramic membranes or ZrO 2 A ceramic membrane;
the conductive film bottom layer comprises a first conductive compound and zirconia;
the conductive film facing layer comprises a second conductive compound and copper oxide;
the first and second electrically conductive composites comprise an electrically conductive polymer, antimony doped tin dioxide, and graphite.
2. The composite conductive film according to claim 1, wherein the mass ratio of the conductive polymer, the antimony-doped tin dioxide and the graphite in the first conductive composite is 80-100: 15 to 30:0.5 to 1;
the mass ratio of the conductive polymer to the antimony-doped tin dioxide to the graphite in the second conductive compound is 80-100: 30 to 35:0.4 to 0.6.
3. The composite conductive film according to claim 1 or 2, wherein the conductive polymer comprises one or more of polypyrrole, polyacetylene, polythiophene, and polyaniline.
4. The composite conductive film according to claim 3, wherein the mass ratio of the first conductive compound to zirconia is 8 to 12:1;
the mass ratio of the second conductive compound to the copper oxide is (15) - (20): 1.
5. the composite conductive film according to claim 1 or 4, wherein the thickness of the bottom layer of the conductive film is 200 to 400 μm;
the thickness of the conductive film surface layer is 50 to 100 mu m.
6. The method for producing a composite conductive film according to any one of claims 1 to 5, comprising the steps of:
first mixing a first conductive compound, zirconium oxide and a first dispersing agent to obtain first slurry;
secondly, mixing a second conductive compound, copper oxide and a second dispersing agent to obtain second slurry;
coating the first slurry on the surface of a substrate, and then carrying out first calcination to obtain a bottom layer of the conductive film;
and coating a second slurry on the surface of the bottom layer of the conductive film, and then carrying out second calcination to obtain the composite conductive film.
7. The method of claim 6, wherein the first and second dispersants each comprise terpineol, ethylcellulose, and castor oil;
the mass ratio of the terpineol, the ethyl cellulose and the castor oil in the first dispersant and the second dispersant is independently 20 to 30:1:3 to 5.
8. The production method according to claim 6 or 7, wherein the mass ratio of the first conductive compound to the first dispersant is 1:2 to 3;
the mass ratio of the second conductive compound to the second dispersant is 1:3 to 5.
9. The preparation method according to claim 6, wherein the temperature of the first calcination is 700 to 800 ℃ and the time is 100 to 120min;
the temperature of the second calcination is 800 to 900 ℃, and the time is 150 to 200min.
10. The composite conductive film according to any one of claims 1 to 5 or the composite conductive film prepared by the preparation method according to any one of claims 6 to 9, and the application of the composite conductive film in sewage treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210220088.2A CN114432908B (en) | 2022-03-08 | 2022-03-08 | Composite conductive film and preparation method and application thereof |
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| CA2273696A1 (en) * | 1998-06-05 | 1999-12-05 | Nissan Chemical Industries, Ltd. | Organic-inorganic composite conductive sol and process for producing the same |
| WO2007007343A2 (en) * | 2005-07-14 | 2007-01-18 | Ben Gurion University Of The Negev Research And Development Authority | Composite membranes and methods for their preparation |
| CN101848962A (en) * | 2007-10-23 | 2010-09-29 | Skc株式会社 | Polythiophene-based conductive polymer membrane |
| CN102671551A (en) * | 2011-03-18 | 2012-09-19 | 中国科学院大连化学物理研究所 | Electro-conductive micro-filtration membrane and preparation method thereof |
| CN108211820A (en) * | 2018-01-29 | 2018-06-29 | 浙江工商大学 | A kind of Conductive inorganic ceramic membrane materials and preparation method |
| CN113764121A (en) * | 2021-09-18 | 2021-12-07 | 西安电子科技大学 | Antimony-doped tin dioxide conductive film and preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2273696A1 (en) * | 1998-06-05 | 1999-12-05 | Nissan Chemical Industries, Ltd. | Organic-inorganic composite conductive sol and process for producing the same |
| WO2007007343A2 (en) * | 2005-07-14 | 2007-01-18 | Ben Gurion University Of The Negev Research And Development Authority | Composite membranes and methods for their preparation |
| CN101848962A (en) * | 2007-10-23 | 2010-09-29 | Skc株式会社 | Polythiophene-based conductive polymer membrane |
| CN102671551A (en) * | 2011-03-18 | 2012-09-19 | 中国科学院大连化学物理研究所 | Electro-conductive micro-filtration membrane and preparation method thereof |
| CN108211820A (en) * | 2018-01-29 | 2018-06-29 | 浙江工商大学 | A kind of Conductive inorganic ceramic membrane materials and preparation method |
| CN113764121A (en) * | 2021-09-18 | 2021-12-07 | 西安电子科技大学 | Antimony-doped tin dioxide conductive film and preparation method and application thereof |
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