CN110327789B - Carbon nano tube/nano fiber conductive composite film and preparation method thereof - Google Patents
Carbon nano tube/nano fiber conductive composite film and preparation method thereof Download PDFInfo
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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
-
- 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
- B01D71/021—Carbon
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to the technical field of films, and provides a carbon nano tube/nano fiber conductive composite film and a preparation method thereof. The one-dimensional nanofiber non-woven fabric prepared by the electrostatic spinning process is used as a supporting layer, and the carbon nanotubes are used as a separating layer on the cross-linking of the supporting layer, so that the conductive film with the mesh-shaped pore structure formed by interweaving the one-dimensional nanomaterials is constructed. The membrane aperture of the related composite membrane is controllable from microfiltration to ultrafiltration, and the membrane morphology comprises a flat membrane, a hollow fiber membrane and a roll-type membrane. The composite membrane has the main advantages and beneficial effects that: the preparation method has the advantages of simple preparation steps, good permeability and mechanical strength, good hydrophilicity and conductivity, and easy large-scale production and application.
Description
Technical Field
The invention relates to a carbon nano tube/nano fiber conductive composite film and a preparation method thereof, belonging to the technical field of films.
Background
The membrane separation technology is a high-efficiency, energy-saving, simple and convenient phase separation technology, and is widely applied to aspects of sewage advanced treatment, household drinking water purification, resource recycling and the like in the field of water treatment. However, the existing separation membrane has the problems of mutual contradiction between water permeability and separation capacity, serious membrane pollution, single membrane function and the like, and further development and application of a membrane separation technology are seriously restricted.
Researches find that the separation membrane prepared based on the carbon nano tube presents a one-dimensional nano material interwoven into a reticular membrane structure and mutually communicated membrane pore paths, and has the advantages of high porosity, low pore bending degree and high permeability. And because the carbon nano tube has excellent conductive performance, the membrane pollution can be effectively slowed down and the contradiction relation between the membrane permeability and the separation capacity can be relieved by an electric auxiliary (electrostatic repulsion, electric enhanced adsorption, electrochemical oxidation and the like) -membrane filtration coupling process, and meanwhile, the electric auxiliary process hopefully endows the carbon nano tube separation membrane with a new function and can effectively relieve the problems of the membrane separation technology at present. There are three main types of separation membranes currently studied based on carbon nanotubes: first, a pure carbon nanotube film assembled by a pure carbon nanotube material; secondly, the carbon nano tube is uniformly mixed with other film-making materials (polymer materials, ceramic film materials and the like) to prepare a mixed matrix film; thirdly, the carbon nano tube is used as a separation layer and coated on the composite membrane prepared on the supporting layer matrix. However, the existing separation membranes based on carbon nanotubes have some problems, which affect the performance and application of the separation membranes. For example: the pure carbon nanotube film has the problems of high preparation cost, poor mechanical strength and difficult application; the carbon nano tube in the mixed matrix carbon nano tube film is seriously coated by other film materials, so that the advantages of the carbon nano tube material are covered; the permeability of the carbon nanotube composite membrane is limited by the supporting layer matrix, and the structural advantage of the carbon nanotube as a one-dimensional nano material cannot be exerted.
Disclosure of Invention
The invention provides the carbon nano tube/nano fiber composite separation membrane which is simple, efficient and easy for large-scale production aiming at the defects of the existing carbon nano tube separation membrane preparation technology and has huge research and market prospects based on the carbon nano tube separation membrane. The invention adopts the non-woven fabric formed by the one-dimensional nano-fiber as the supporting layer, and the carbon nano-tube is used as the separating layer on the cross-linking of the supporting layer, so that the whole composite membrane keeps a reticular pore structure formed by interweaving the one-dimensional nano-materials.
The technical scheme of the invention is as follows:
a composite separation membrane based on carbon nano tubes/nano fibers is divided into a supporting layer and a functional layer, the nano fibers prepared by electrostatic spinning are used as the supporting layer, the carbon nano tubes are used as a separation layer, the carbon nano tubes cover the surfaces of the nano fibers, and the carbon nano tubes are jointly cross-linked and fixed through a cross-linking agent 1 and a cross-linking agent 2; the carbon nano tube and the nano fiber are both one-dimensional linear materials, the two linear materials construct a three-dimensional reticular pore structure separation membrane, and the linear materials are mutually wound in a staggered mode to enhance the interaction between the supporting layer and the separation layer, so that a stable membrane structure is formed.
The supporting layer material described in the scheme can be synthetic polymer macromolecule, natural macromolecule, inorganic alkoxide, ceramic precursor, etc., including but not limited to, and the material suitable for electrostatic spinning can be used for preparing the nanofiber supporting layer.
Crosslinking agent 1 and crosslinking agent 2: polyacrylamide and succinic acid, polyvinyl alcohol and glutaraldehyde, polyvinyl alcohol and glutaric acid, phenolic resins and oxalic acid.
The membrane forms include three types, namely a flat membrane, a hollow fiber membrane and a roll-type membrane.
A preparation method based on a carbon nano tube/nano fiber composite separation membrane comprises the following steps:
first, preparation of a nanofiber support layer
(1) Dissolving the spinning material serving as the supporting layer in a corresponding solvent to prepare spinning solution with the mass fraction of 10-20%, and performing electrostatic spinning; slowly injecting the spinning solution through a trace sample injection pump, transferring and stretching liquid drops to a receiving device under the action of an electrostatic field to form nano fibers, regulating and controlling electrostatic spinning voltage density to be 1kV/cm, regulating and controlling spinning distance to be within the range of 10cm-20cm, regulating and controlling spinning time to be 4-20h according to concentration, and obtaining a corresponding nano fiber supporting layer from the receiving device;
wherein, according to different membrane forms, the specific operations are as follows:
flat membrane: adopting a roller nanofiber collector or a flat nanofiber collector to receive electrostatic spinning to prepare nanofibers, and directly taking down a hot-press forming flat supporting layer from the surface of the collector after collection is finished;
hollow fiber membranes: a dynamic continuous filament collector is adopted, in the electrostatic spinning filamentation process, after the continuous filament collector is controlled to pass through a receiving nanofiber area at a fixed speed, the filament collector is conveyed to a heating chamber, and the nanofiber is heated and stably shrunk according to the heat resistance of the material; then immersing the filament collector into 0.1mol/L dilute acid solution or copper salt solution for 5-60min, and then drawing out the filament collector to obtain a hollow fiber supporting layer;
roll-up membrane: adopting a conductive roll type central pipe network as a nanofiber collector, carrying out hot press molding on the central pipe network and the nanofibers after collection is finished, fixing the non-woven fabric membrane by gluing, and cooling to room temperature to obtain a roll type membrane supporting layer;
second, electrostatic spraying is carried out to prepare a carbon nano tube functional layer
Dispersing the carbon nano tube acidified by the mixed acid into water to prepare 5-10mg/mL dispersion liquid, wherein the volume ratio of the mixed acid is 3: 1 of 95-98wt.% concentrated sulfuric acid and 65-68wt.% concentrated nitric acid; then, carrying out electrostatic spraying on the nanofiber supporting layer within the range of regulating and controlling the voltage density to be 1kV/cm and the spinning distance to be 10-20 cm;
third step, crosslinking of the carbon nanotube/nanofiber composite film
Taking down the prepared and molded composite membrane, soaking the composite membrane in a mixed solution of a cross-linking agent 1 and a cross-linking agent 2, and adding 2M hydrochloric acid to adjust the pH value to 2; taking out, washing with deionized water, and drying and curing at 60 deg.C.
The invention has the beneficial effects that:
(1) the separation membrane constructed based on the all-dimensional nano material has the advantages of a net-shaped through hole structure, high membrane porosity, low hole tortuosity and high effective porosity, the membrane permeability is enhanced by the advantages, and the flux of the separation membrane constructed based on the all-dimensional nano material is 2-10 times higher than that of the separation membrane with the same pore size in the market.
(2) Based on the assembly construction of one-dimensional nano materials with extremely high length-diameter ratio, the separation membrane disclosed by the invention has excellent flexibility and mechanical strength.
(3) The interface of the separation layer and the support layer is formed by mutually winding two one-dimensional linear nano materials in a staggered way, so that the interaction between the support layer and the separation layer is enhanced, and the function of stabilizing the whole membrane structure is achieved
(4) The carbon nanotube separating layer is prepared by an electrostatic spraying process, has a porosity of more than 80%, and is beneficial to reducing mass transfer resistance and improving membrane permeability.
(5) The conductive characteristic of the carbon nano tube of the separation layer is kept, and the coupling with other processes is facilitated.
(6) The carbon nano tube is fixed by the cross-linking agent, so that the stability of the separating layer is ensured.
(7) The method is flexible and controllable, can prepare separation membranes with various forms and is easy for large-scale production and application.
Drawings
Fig. 1 is a scanning electron microscope image of a carbon nanotube/nanofiber composite membrane support layer.
FIG. 2 is a scanning electron microscope image of a carbon nanotube/nanofiber composite membrane separation layer.
Detailed Description
The embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to the following embodiments.
Example 1: preparation of carbon nanotube/PAN nanofiber composite flat membrane
First, preparing a nanofiber substrate by electrostatic spinning
Dissolving high molecular polymer Polyacrylonitrile (PAN) serving as a substrate in N, N-Dimethylformamide (DMF) to prepare spinning solution with the mass fraction of 15%, regulating and controlling the voltage density to be about 1kV/cm, the spinning distance to be within the range of 10-20cm, regulating and controlling the spinning time to be 10h according to the concentration, obtaining a corresponding nanofiber substrate from a receiving device, and carrying out hot pressing at 150 ℃ to obtain the flat nanofiber supporting layer.
Second, electrostatic spraying is carried out to prepare a carbon nano tube functional layer
And (3) dispersing the carbon nano tubes with the tube diameters of 60-100nm in water after acidification of mixed acid to prepare 5mg/mL dispersion, and then carrying out electrostatic spraying on the nanofiber substrate for 6 hours within the range of 10-20cm under the condition of regulating and controlling the voltage density to be about 1 kV/cm.
Third step, crosslinking of the carbon nanotube/PAN nanofiber composite membrane
Taking down the prepared and molded composite membrane, soaking the composite membrane for 1h in a mixed solution with mass concentration of polyacrylamide (0.2%) and oxalic acid (1%), and adding 2M hydrochloric acid to adjust the pH value to acidity. Taking out, washing with deionized water, and drying and curing at 60 deg.C.
As a result: the prepared carbon nano tube/PAN nano fiber composite flat membrane supporting layer and the separating layer both present a reticular through hole structure, the aperture of the supporting layer is in the range of 1-2 mu m, and the aperture of the composite membrane is about 300 nm. And because PAN thermal stability is better, the high-temperature thermal compression shrinkage nanofiber is facilitated, so that the carbon nanotube/nanofiber composite membrane prepared based on the PAN material has optimal mechanical strength and stability.
Example 2 preparation of carbon nanotube/PAN nanofiber composite hollow fiber Membrane
First, preparing a nanofiber substrate by electrostatic spinning
Dissolving high molecular polymer PAN serving as a substrate in DMF (dimethyl formamide) to prepare spinning solution with the mass fraction of 15%, regulating and controlling the voltage density to be about 1kV/cm, controlling the spinning distance to be within 10cm, using a stainless steel filament collector as a receiving device, regulating and controlling the spinning time to be 6h according to the concentration, and obtaining the corresponding nanofiber hollow fiber supporting layer from the receiving device.
Second, electrostatic spraying is carried out to prepare a carbon nano tube functional layer
And (2) dispersing the carbon nano tubes with the tube diameters of 60-100nm in water after acidification of mixed acid to prepare 5-10mg/mL dispersion, and then carrying out electrostatic spraying on the nanofiber substrate for 6h within the range of 10-20cm under the condition of regulating and controlling the voltage density to be about 1 kV/cm.
Third step, crosslinking of the carbon nanotube/PAN nanofiber composite membrane
Taking down the prepared and formed composite membrane and the collector, soaking the composite membrane in a mixed solution with the mass concentration of polyvinyl alcohol (0.2%) and glutaric acid (1%) for 1h, and adding 2M hydrochloric acid to adjust the pH value to acidity. Taking out, washing with deionized water, and drying and curing at 60 deg.C. The membrane and collector were then placed together in an oven and pre-oxidized at 250 ℃. And after pre-oxidation, putting the membrane and the collector together in a 1M copper sulfate solution for soaking for 10min, drawing the hollow fiber membrane out of the filament collector, washing with deionized water and drying to obtain the carbon nanotube/PAN nanofiber composite hollow fiber membrane.
As a result: the prepared carbon nano tube/PAN nano fiber composite hollow fiber membrane supporting layer and the separating layer both present a reticular through hole structure, the aperture of the supporting layer is in the range of 1-2 mu m, and the aperture of the composite membrane is about 300 nm.
Example 3 preparation of carbon nanotube/PVDF nanofiber composite Flat Membrane
First, preparing a nanofiber substrate by electrostatic spinning
Dissolving high molecular polymer polyvinylidene fluoride (PVDF) as a substrate into a mixed solution (volume ratio is 9:1) of DMF and acetone to prepare a spinning solution with the mass fraction of 18%, regulating and controlling the voltage density to be about 1kV/cm, the spinning distance to be within 10cm, regulating and controlling the spinning time to be 10h according to the concentration, carrying out hot pressing at 80 ℃, and obtaining the corresponding flat nano-fiber membrane substrate from a receiving device.
Second, electrostatic spraying is carried out to prepare a carbon nano tube functional layer
Dispersing the carbon nano-tubes with the tube diameters of 10-20nm after acidification of mixed acid in water to prepare 5-10mg/mL dispersion, and then carrying out electrostatic spraying on the nano-fiber substrate for 6h within the range of 10-20cm under the condition of regulating and controlling the voltage density to be about 1 kV/cm.
Step three, crosslinking of the carbon nanotube/PVDF nanofiber composite membrane
Taking down the prepared and molded composite membrane, soaking the composite membrane in an ethanol solution (0.2%) with the mass concentration of phenolic resin for 1 hour, and adding oxalic acid to adjust the pH value to acidity. Taking out, washing with ethanol, and drying and curing at 60 deg.C.
As a result: the prepared carbon nanotube/PVDF nanofiber composite flat membrane supporting layer and the separation layer both present a reticular through hole structure, the aperture of the supporting layer is within the range of 400-600nm, and the aperture of the composite membrane is about 70 nm.
Example 4 preparation of carbon nanotubes/Al2O3Nano fiber composite flat membrane
First, preparing a nanofiber substrate by electrostatic spinning
Adding formic acid and acetic acid into high-purity water according to the mass ratio of 1:1, then adding a certain amount of Al powder, heating and stirring until the Al powder is completely dissolved, then filtering by using a glass fiber membrane to remove residues, preparing Al gel with the mass fraction of about 10%, then adding a certain amount of polyvinylpyrrolidone to increase the viscosity of the solution, regulating and controlling the voltage density to be about 1kV/cm, the spinning distance to be within the range of 10cm, regulating and controlling the spinning time to be 10h according to the concentration, and obtaining the corresponding nanofiber membrane substrate from a receiving device. Then taking the substrate down to calcine at 800 ℃, and keeping the temperature for two hours to obtain Al2O3A nanofiber membrane substrate.
Second, electrostatic spraying is carried out to prepare a carbon nano tube functional layer
Dispersing the acidified carbon nano-tube with the pipe diameter of 60-100nm of mixed acid in water to prepare 5-10mg/mL dispersion, and then regulating and controlling the voltage density to be about 1kV/cm, and calcining the Al2O3The nanofiber membrane substrate is fixed on a receiving device, and electrostatic spraying is carried out on the nanofiber substrate within the spinning distance of 10-20cm for 6 hours.
Third step, crosslinking of the carbon nanotube/nanofiber composite film
Taking down the prepared and molded composite membrane, soaking the composite membrane in an ethanol solution (0.2%) with the mass concentration of phenolic resin for 1 hour, and adding oxalic acid to adjust the pH value to acidity. Taking out, washing with ethanol, and drying and curing at 60 deg.C.
As a result: prepared carbon nano tube/Al2O3The support layer and the separation layer of the nanofiber composite hollow fiber membrane both present a reticular through hole structure, the aperture of the support layer is within the range of 300-500nm, and the aperture of the composite membrane is about 100 nm.
Example 5: preparation of carbon nanotube/PAN nanofiber composite roll-up membrane
First, preparing a nanofiber substrate by electrostatic spinning
Dissolving high-molecular PAN serving as a substrate in DMF (dimethyl formamide) to prepare spinning solution with the mass fraction of 15%, regulating and controlling the voltage density to be about 1kV/cm, the spinning distance to be within the range of 10-20cm, regulating and controlling the spinning time to be 10h according to the concentration, taking a stainless steel coil pipe network as a receiving device, fixing a non-woven fabric membrane by gluing and hot pressing after the spinning is finished, and then cooling to room temperature to obtain the corresponding roll type nanofiber supporting layer.
Second, electrostatic spraying is carried out to prepare a carbon nano tube functional layer
And (3) dispersing the carbon nano tubes with the tube diameters of 60-100nm in water after acidification of mixed acid to prepare 5mg/mL dispersion, and then carrying out electrostatic spraying on the nanofiber substrate for 6 hours within the range of 10-20cm under the condition of regulating and controlling the voltage density to be about 1 kV/cm.
Third step, crosslinking of the carbon nanotube/PAN nanofiber composite membrane
Taking down the prepared and molded composite membrane, soaking the composite membrane for 1h in a mixed solution with mass concentration of polyacrylamide (0.2%) and oxalic acid (1%), and adding 2M hydrochloric acid to adjust the pH value to acidity. Taking out, washing with deionized water, and drying and curing at 60 deg.C.
As a result: the prepared carbon nano tube/PAN nano fiber composite roll-type membrane presents a net-shaped through hole structure, and the aperture of the composite membrane is about 300 nm.
Claims (1)
1. A preparation method based on a carbon nanotube/nanofiber composite separation membrane is characterized in that the carbon nanotube/nanofiber composite separation membrane is divided into a supporting layer and a functional layer, nanofibers prepared through electrostatic spinning are used as the supporting layer, carbon nanotubes are used as the separation layer, the carbon nanotubes cover the surfaces of the nanofibers, and the carbon nanotubes are fixed through common crosslinking of a crosslinking agent 1 and a crosslinking agent 2; the carbon nano tube and the nano fiber are both one-dimensional linear materials, the two linear materials construct a three-dimensional reticular pore structure separation membrane, and the linear materials are mutually wound in a staggered way to enhance the interaction between the supporting layer and the separation layer, so that a stable membrane structure is formed; the crosslinking agent 1 and the crosslinking agent 2 are as follows: polyacrylamide and succinic acid, polyvinyl alcohol and glutaraldehyde;
the method comprises the following steps:
first, preparation of a nanofiber support layer
(1) Dissolving the spinning material serving as the supporting layer in a corresponding solvent to prepare spinning solution with the mass fraction of 10-20%, and performing electrostatic spinning; slowly injecting the spinning solution through a trace sample injection pump, transferring and stretching liquid drops to a receiving device under the action of an electrostatic field to form nano fibers, regulating and controlling electrostatic spinning voltage density to be 1kV/cm, regulating and controlling spinning distance to be within the range of 10cm-20cm, regulating and controlling spinning time to be 4-20h according to concentration, and obtaining a corresponding nano fiber supporting layer from the receiving device;
wherein, according to different membrane forms, the specific operations are as follows:
flat membrane: adopting a roller nanofiber collector or a flat nanofiber collector to receive electrostatic spinning to prepare nanofibers, and directly taking down a hot-press forming flat supporting layer from the surface of the collector after collection is finished;
hollow fiber membranes: a dynamic continuous filament collector is adopted, in the electrostatic spinning filamentation process, after the continuous filament collector is controlled to pass through a receiving nanofiber area at a fixed speed, the filament collector is conveyed to a heating chamber, and the nanofiber is heated and stably shrunk according to the heat resistance of the material; then immersing the filament collector into 0.1mol/L dilute acid solution or copper salt solution for 5-60min, and then drawing out the filament collector to obtain a hollow fiber supporting layer;
roll-up membrane: adopting a conductive roll type central pipe network as a nanofiber collector, carrying out hot press molding on the central pipe network and the nanofibers after collection is finished, fixing the non-woven fabric membrane by gluing, and cooling to room temperature to obtain a roll type membrane supporting layer;
second, electrostatic spraying is carried out to prepare a carbon nano tube functional layer
Dispersing the carbon nano tube acidified by the mixed acid into water to prepare 5-10mg/mL dispersion liquid, wherein the volume ratio of the mixed acid is 3: 1 of 95-98wt.% concentrated sulfuric acid and 65-68wt.% concentrated nitric acid; then, carrying out electrostatic spraying on the nanofiber supporting layer within the range of regulating and controlling the voltage density to be 1kV/cm and the spinning distance to be 10-20 cm;
third step, crosslinking of the carbon nanotube/nanofiber composite film
Taking down the prepared and molded composite membrane, soaking the composite membrane in a mixed solution of a cross-linking agent 1 and a cross-linking agent 2, and adding 2M hydrochloric acid to adjust the pH value to 2; taking out and washing with deionized water, 60oAnd C, drying and curing.
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