CN109529635B - Composite material of graphene, nano-fiber and nano-particle and preparation method thereof - Google Patents
Composite material of graphene, nano-fiber and nano-particle and preparation method thereof Download PDFInfo
- Publication number
- CN109529635B CN109529635B CN201811419793.5A CN201811419793A CN109529635B CN 109529635 B CN109529635 B CN 109529635B CN 201811419793 A CN201811419793 A CN 201811419793A CN 109529635 B CN109529635 B CN 109529635B
- Authority
- CN
- China
- Prior art keywords
- graphene
- pressure ring
- pcl
- ethyl alcohol
- absolute ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/48—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The utility model provides a preparation facilities of graphite alkene and nano-fiber and nano-particle's combined material, includes barrel (3), goes up clamping ring (2), goes up clamping ring rubber (1), pushes down clamping ring rubber (4), pushes down clamping ring (5), barrel (6) down, bottom plate (7), gas outlet (8), outlet duct (9), cushion ball (12), lower liquid pipe (13), exhaust tube (10), air extractor (11). Also included are composite materials prepared using the preparation apparatus, and methods of using the preparation apparatus.
Description
Technical Field
The invention relates to the technical field of graphene composite materials, in particular to a composite material of graphene, nano fibers and nano particles, and a preparation method and a device thereof.
Background
Graphene is a two-dimensional material consisting of carbon atoms and having a thickness of only one atom, has very excellent physicochemical properties, such as excellent mechanical properties, high electrical conductivity, good thermal conductivity and the like, and is considered to be one of the most potential nano materials at present. As a one-dimensional carbon nano material, the carbon nano fiber has the advantages of good mechanical property, larger specific surface area, good chemical stability and the like, and the special properties enable the carbon nano fiber to be widely applied to the fields of catalyst carriers, polymer nano composite materials, flexible substrate materials of energy conversion and storage devices and the like. Taking the graphene microchip as an example, the graphene microchip not only has better physical properties and electrical properties, but also can be compounded with other materials to further improve the properties of other materials.
The electrostatic spinning is a simple and effective technology for preparing carbon nanofibers, and the electrostatic spinning carbon nanofiber membrane with a three-dimensional porous structure and a high specific surface area can be prepared by spinning a polymer solution through high-voltage static electricity, and then carrying out pre-oxidation and high-temperature carbonization. The method adopts an electrostatic spinning process, carries out spinning on polyacrylonitrile solution, and prepares the polyacrylonitrile nanofiber membrane through pre-oxidation.
Document CN105297405A describes a composite method, in which graphene oxide is coated on polyacrylonitrile nanofibers by a solution soaking method, and then graphene/carbon nanofiber composite membranes are prepared by high-temperature carbonization, and the graphene/carbon nanofiber composite membranes are used as a base material to further prepare high-performance composite materials. The method has obvious defects that firstly, the method is high in temperature, secondly, the mode of adding the graphene is too simple, the adding amount is insufficient, the compounding condition is not uniform, and a good carrier is difficult to provide for uniform dispersion of the cobalt zinc sulfide nano particles.
The cobalt zinc sulfide is a typical metal sulfide, and has good self conductivity and high theoretical capacity value. Compared with common materials, the cobalt zinc sulfide has very high conductivity and theoretical lithium storage capacity value, and is widely concerned and applied in the fields of catalysis, super capacitors, lithium ion battery electrode materials and the like. Pure cobalt zinc sulfide particles are easy to agglomerate, which is the biggest problem restricting the application of the cobalt zinc sulfide particles, so that active sites of the cobalt zinc sulfide particles cannot be fully exposed, the catalytic property and the cycling stability of energy storage of the cobalt zinc sulfide particles are seriously influenced, the prepared material with serious agglomeration cannot be reflected, and the superior performance of the material cannot be reflected. Therefore, the cobalt zinc sulfide and the nano material with excellent stability are effectively compounded, the stability of the cobalt zinc sulfide is fully improved, and the method has important significance for the cobalt zinc sulfide.
How to effectively disperse cobalt zinc sulfide and effectively disperse graphene in a porous material to promote uniform adhesion is an effective way, but the aforementioned CN105297405A is obviously insufficient, firstly, graphene is only attached in a soaking way, and uniformity is a great problem of how to attach the graphene, so that it is difficult to perform a good function on cobalt zinc sulfide adhesion, and the carbonization way adopted is too high in temperature, so that carbonization is performed at such a high temperature, which in fact has a great influence on the integrity of a fiber structure, and a great number of large voids are actually generated, which is extremely disadvantageous for cobalt zinc sulfide dispersion and uniform adhesion; the document of electrostatic spinning method for preparing polycaprolactone/graphene composite material nanofiber reported by the Chinese academy of sciences provides a method for dispersing graphene in an electrospinning film, but is limited by adding graphene into electrospinning liquid, the concentration of the graphene is only about 1% at most, and in the electron microscope picture in the text, the influence of adding the graphene in the electrospinning link on the fiber structure is great, the fiber structure has great irregularity, and the structure has insufficient benefits for uniform dispersion of cobalt zinc sulfide and cannot be used as a good carrier.
In the prior art, no research and analysis are carried out on how to prepare a good carrier of cobalt zinc sulfide, and the performance of the cobalt zinc sulfide is difficult to reflect due to the insufficient dispersity.
Disclosure of Invention
The invention aims to provide a good composite material to overcome the defects that the performance of cobalt zinc sulfide in the prior art is still limited, the dispersion degree of the cobalt zinc sulfide in a microporous carrier is insufficient, and the good performance is not exerted. Compared with the prior art, the invention effectively provides an excellent carrier for the dispersion of cobalt zinc sulfide by effectively attaching the graphene nanoplatelets with specific sizes in the PCL electrospun membrane under negative pressure and then carrying out low-temperature micro-carbonization.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation device of a composite material of graphene, nano-fibers and nano-particles comprises the following components: go up barrel, go up clamping ring rubber, lower clamping ring rubber, barrel, bottom plate, gas outlet, outlet duct, buffering ball, lower liquid pipe, exhaust tube, air extractor down. The upper cylinder body is positioned on the upper pressure ring, the bottommost part of the upper cylinder body is provided with an upper flange, the innermost side of the upper pressure ring is provided with an upper groove matched with the upper flange, and the upper cylinder body and the upper pressure ring are tightly matched with each other through the upper flange and the upper groove; go up clamping ring rubber and be the ring form on being located the clamping ring lower surface, clamping ring rubber is located down the clamping ring upper surface and is the ring form down, it is the even thin layer of thickness between 600um-1000um with lower clamping ring rubber to go up clamping ring rubber bonding at last clamping ring lower surface, will the clamping ring upper surface is glued down to lower clamping ring rubber.
The projection of the upper pressing ring rubber and the projection of the lower pressing ring rubber in the overlook direction are completely overlapped, and a completely flattened PCL electrospun membrane is clamped between the upper pressing ring rubber and the lower pressing ring rubber.
The lower cylinder body is positioned below the lower pressing ring, the uppermost part of the lower cylinder body is provided with a circle of lower grooves, the innermost side of the lower pressing ring is provided with lower flanges matched with the lower grooves, the lower cylinder body and the lower pressing ring are tightly matched with the lower grooves through the lower flanges, the length of the lower flanges in the Z-axis direction is at least 1-2cm, and the lower grooves are provided with depths matched with the lower flanges.
The bottom plate and the lower barrel are integrally formed or are matched with each other to be tightly connected, and sealant is coated at the joint; the air outlet is vertical to the side wall of the lower cylinder, and the distance from the central axis to the bottom plate is not more than 10 cm; the air extractor is provided with a display panel and is used for displaying whether the air extractor is started or not at present and the flow of the extracted air.
The upper cylinder, the upper compression ring, the lower cylinder, the bottom plate and the air outlet are made of transparent or semitransparent hard polymeric materials; the air outlet pipe, the buffer ball, the liquid discharging pipe and the air exhaust pipe are made of transparent or semitransparent materials; and an anti-backflow sheet is arranged in the middle of the liquid outlet pipe and can only be opened downwards.
Further: the upper pressing ring rubber and the lower pressing ring rubber are made of scratch-resistant heat-vulcanized butyl rubber, and the surfaces of the upper pressing ring rubber and the lower pressing ring rubber are provided with uneven net-shaped grains; the upper cylinder, the upper pressure ring, the lower cylinder, the bottom plate, the air outlet and the anti-backflow sheet are made of polypropylene or polycarbonate materials; the air outlet pipe, the buffer ball, the liquid discharging pipe and the air exhaust pipe are made of epoxy resin; the air extractor is provided with a plurality of gears, the air extraction volume is between 0.5 and 5L/min, and the 12V direct current power supply is realized through alternating current conversion.
The preparation method of the composite material of graphene, nano-fibers and nano-particles is implemented by using the preparation device of the composite material of graphene, nano-fibers and nano-particles, and is characterized by comprising the following steps of:
1) preparing an electrospinning membrane: and (3) selecting a proper amount of PCL fiber, adding the PCL fiber into 100ml of analytically pure chloroform, and performing ultrasonic dispersion for 15-30min to obtain the PCL fiber chloroform dispersion liquid with the mass percentage of 3-7%.
Selecting the electrospinning voltage of 10-15kV, the extrusion speed of 2-4ml/h, the receiving distance of 20-30cm, the electrospinning time of 2h and the ambient temperature of 4-8 ℃ to obtain the PCL electrospinning membrane.
2) A film clamping step: selecting the obtained PCL electrospun membrane with the area larger than that of the upper pressing ring (2) or the lower pressing ring (5), sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for at least 1 time, and after completely airing, tensioning and clamping the cleaned PCL electrospun membrane between the upper pressing ring rubber (1) and the lower pressing ring rubber (4) to ensure that the PCL electrospun membrane is free of wrinkles.
3) Preparing a graphene nanoplatelet dispersion liquid: a large number of prefabricated expanded graphite sheet layers are used as raw materials, and graphene nanoplatelets are generated through ultrasonic stripping for more than 1h in absolute ethyl alcohol.
Supplementing the solvent absolute ethyl alcohol of the graphene nanoplatelets to more than 200ml, carrying out high-intensity ultrasonic oscillation for 3-5min, immediately discarding the upper half of dispersion liquid, and repeating the above process for at least 5-10 times until the average radial size of the graphene nanoplatelets is higher than 5-10 um.
4) A negative pressure attaching step: conducting ultrasonic dispersion on 150ml of chloroform dispersion liquid containing 5-10% of graphene nanoplatelets with the average radial dimension higher than 5-10um by mass percent for 1-2min, introducing the chloroform dispersion liquid into the upper cylinder (3) at a very slow speed, after pouring, pumping the air pump for 2-5s at the flow rate of 0.5-1.5L/min, and stopping circulating for 5-8s repeatedly until no obvious liquid dripping of the PCL electrospun membrane is observed through the lower cylinder; a waste liquid cylinder is used for receiving and recycling the liquid flowing out from the lower liquid pipe (13); repeating the previous operation of the step (4) for 10-20 times; cutting off a circular part attached by the graphene from the electrospun membrane attached with the graphene nanoplatelets, respectively cleaning the silicon wafer for at least 1 time by using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol in sequence, and completely airing to obtain the graphene PCL electrospun membrane composite material.
5) Micro-carbonization: the graphene PCL electrospun membrane composite material is placed in a heating container and is leveled, and is subjected to micro-carbonization for 30-90min at the temperature of 210-225 ℃.
6) A hydrothermal reaction step: 6) dissolving cobalt nitrate, zinc nitrate, thiourea and urea in a sufficient amount of 1: 9 volume ratio of absolute ethyl alcohol and deionized water, and reacting under strong stirring; repeatedly heating and cooling to 4 ℃ for at least three times, and removing the precipitated biuret to obtain a salt solution.
And (3) putting 100-150ml of saline solution and 1-3g of the PCL electrospun membrane composite material into a hydrothermal kettle, reacting for 16-24h at the temperature of 200-220 ℃, and sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for 3-5 times to obtain the cobalt zinc sulfide/graphene nanoplatelets/PCL electrospun membrane composite material.
The cobalt zinc sulfide/graphene microchip/PCL electrospun membrane composite material is prepared by the preparation method of the composite material of graphene, nano-fibers and nano-particles, and is characterized by comprising the following properties: based on a PCL electrospun membrane after partial carbonization, graphene micro-sheets with the average radial size higher than 5-10um are dispersed among PCL fibers, cobalt zinc sulfide nano-particles are also dispersed among the PCL fibers, the mass percentage of the graphene micro-sheets in the composite material is more than 3%, and the mass percentage of the cobalt zinc sulfide nano-particles in the composite material is more than 5%.
Compared with the prior art, the invention has the following beneficial effects: 1) compared with the prior art, the method has the advantages that the negative pressure adsorption mode is innovatively utilized, the graphene microchip with slightly large radial size is effectively loaded, adsorption is enabled to be very effective through repeated adsorption and adhesion of very low negative pressure, conditions are provided for preparation of good carriers, and the prior art does not suggest. 2) The PCL fiber is carbonized at a temperature of more than 150 ℃ but is carbonized at a temperature of more than 225 ℃, but the carbonization process is greatly accelerated at the temperature of more than 225 ℃, but the high-temperature carbonization and the high-temperature carbonization are very unfavorable for the attachment of the carrier, and the temperature of the non-high-speed carbonization stage is adopted, so that the carrier is only carbonized slightly, the structure cannot be greatly damaged, and the subsequent attachment is facilitated. 3) The graphene introduced by the method is not only large in amount but also uniform, so that the adhesion amount of cobalt and zinc sulfide is greatly increased, the amount of cobalt and zinc sulfide adhered to the inner surface of the carrier is increased by a large amount in the same ratio, and the prior art does not disclose or suggest.
Drawings
FIG. 1 is a schematic side sectional view of the structure of the device of the present invention.
In the figure: 1. go up clamping ring rubber, 2, go up the clamping ring, 3, go up the barrel, 4, lower clamping ring rubber, 5, lower clamping ring, 6, lower barrel, 7, bottom plate, 8, gas outlet, 9, outlet duct, 10, exhaust tube, 11, air extractor, 12, buffering ball, 13, downcomer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation device of a composite material of graphene, nano-fibers and nano-particles comprises the following components: the device comprises an upper barrel 3, an upper press ring 2, upper press ring rubber 1, lower press ring rubber 4, a lower press ring 5, a lower barrel 6, a bottom plate 7, an air outlet 8, an air outlet pipe 9, a buffer ball 12, a lower liquid pipe 13, an air exhaust pipe 10 and an air extractor 11; the upper cylinder body is positioned on the upper pressure ring, the bottommost part of the upper cylinder body is provided with an upper flange, the innermost side of the upper pressure ring is provided with an upper groove matched with the upper flange, and the upper cylinder body and the upper pressure ring are tightly matched with each other through the upper flange and the upper groove; the upper pressure ring rubber 1 is positioned on the lower surface of the upper pressure ring and is in a circular ring shape, the lower pressure ring rubber 4 is positioned on the upper surface of the lower pressure ring and is in a circular ring shape, the upper pressure ring rubber 1 and the lower pressure ring rubber 4 are even thin layers with the thickness of 600um/700um/800um/900um/1000um, the upper pressure ring rubber 1 is adhered to the lower surface of the upper pressure ring by glue, and the lower pressure ring rubber 4 is adhered to the upper surface of the lower pressure ring; the upper pressure ring rubber 1 and the lower pressure ring rubber 4 are completely overlapped in the projection in the overlooking direction, and a completely flattened PCL (polycaprolactone) electrospun membrane is clamped between the upper pressure ring rubber and the lower pressure ring rubber; the lower cylinder body is positioned below the lower pressure ring, the uppermost part of the lower cylinder body is provided with a circle of lower grooves, the innermost side of the lower pressure ring is provided with lower flanges matched with the lower grooves, the lower cylinder body and the lower pressure ring are tightly matched with each other through the lower flanges and the lower grooves, the length of the lower flanges in the Z-axis direction is at least 1-2cm, and the lower grooves have the depth matched with the lower flanges; the bottom plate 7 and the lower barrel 6 are integrally formed or are matched with each other to be tightly connected, and sealant is coated at the joint and is 3M glue or polyurethane-based glue; the air outlet 8 is vertical to the side wall of the lower cylinder 6, and the central axis of the air outlet is not more than 10cm away from the bottom plate 7, such as 7/8/9 cm; the air pump 11 is provided with a display panel for displaying whether the air pump is started or not and the flow of the pumped air; the upper cylinder 3, the upper pressure ring 2, the lower pressure ring 5, the lower cylinder 6, the bottom plate 7 and the air outlet 8 are made of transparent or semitransparent hard polymeric materials; the air outlet pipe 9, the buffer ball 12, the liquid outlet pipe 13 and the air exhaust pipe 10 are made of transparent or semitransparent materials; and an anti-backflow sheet is arranged in the middle of the liquid outlet pipe 13 and can only be opened downwards.
The upper compression ring rubber 1 and the lower compression ring rubber 4 are made of scratch-resistant heat-vulcanized butyl rubber, the surfaces of the upper compression ring rubber and the lower compression ring rubber are hardened, and the surfaces of the upper compression ring rubber and the lower compression ring rubber have uneven net-shaped lines and certain surface friction force; the upper cylinder 3, the upper pressure ring 2, the lower pressure ring 5, the lower cylinder 6, the bottom plate 7, the air outlet 8 and the anti-reflux sheet are made of polypropylene or polycarbonate materials, and the transparency is better for clearly seeing the condition of the internal fluid; the air outlet pipe 9, the buffer ball 12, the liquid outlet pipe 13 and the air exhaust pipe 10 are made of epoxy resin, and the epoxy resin has high toughness and is difficult to generate plastic deformation in conventional use; the air extractor has a plurality of gears, the air extraction volume is between 0.5L/min and 5L/min, such as 0.5,1, 1.5,2,2.5,3,3.5 and 4, and the power is supplied by 12V direct current converted by alternating current. The external power supply is 110 or 220V.
Example 2
A method for preparing a graphene/nanofiber/nanoparticle composite material, which is implemented by using the apparatus for preparing a graphene/nanofiber/nanoparticle composite material according to embodiment 1, the method comprising the following steps.
1) Preparing an electrospinning membrane: and (3) selecting a proper amount of PCL fiber, adding the PCL fiber into 100ml of analytically pure chloroform, and performing ultrasonic dispersion for 20min to obtain a PCL fiber chloroform dispersion liquid with the mass percent of 5%.
Selecting the electrospinning voltage of 10kV, the extrusion speed of 2.5ml/h, the receiving distance of 20cm, the electrospinning time of 2h and the ambient temperature of 4 ℃ to obtain the PCL electrospun membrane. Here, the voltage is as low as possible, the speed is as low as possible, and the ambient temperature is high, so that the electrospun membrane with the largest gap is expected to be obtained for preparation for subsequent use.
2) A film clamping step: selecting the obtained PCL electrospun membrane with the area larger than that of the upper pressing ring (2) or the lower pressing ring (5), sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for 3 times, completely airing, tensioning and clamping the cleaned PCL electrospun membrane between the upper pressing ring rubber 1 and the lower pressing ring rubber 4 to ensure that the PCL electrospun membrane is free of wrinkles.
3) Preparing a graphene nanoplatelet dispersion liquid: a large number of prefabricated expanded graphite sheet layers are used as raw materials, and graphene nanoplatelets are generated through ultrasonic stripping for more than 1h in absolute ethyl alcohol. Supplementing the solvent absolute ethyl alcohol of the graphene nanoplatelets to more than 200ml, carrying out high-intensity ultrasonic oscillation for 3min, immediately discarding half of the upper dispersion liquid, and repeating the above process for at least 5 times until the average radial size of the graphene nanoplatelets is higher than 5 um.
4) A negative pressure attaching step: performing ultrasonic dispersion on 120ml of chloroform dispersion liquid containing 5-10% of graphene nanoplatelets with the average radial dimension higher than 5-10um by mass for 1min, introducing the chloroform dispersion liquid into the upper cylinder 3 at a very slow speed, after pouring, pumping the air pump for 3s at the flow rate of 0.6L/min, and stopping circulating the air pump repeatedly for 6s until no obvious liquid dripping of the PCL electrospun membrane is observed through the lower cylinder; a waste liquid cylinder is used for receiving and recycling the liquid flowing out from the lower liquid pipe (13); repeating the previous part of the operation of the step (4) for 15 times; cutting off a circular part attached by the graphene from the electrospun membrane attached with the graphene nanoplatelets, sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for at least 1 time, and completely airing to obtain the graphene PCL electrospun membrane composite material;
5) micro-carbonization: flattening the graphene PCL electrospun membrane composite material in a heating container, and carbonizing for 50min at 210 ℃;
6) a hydrothermal reaction step: 6) dissolving cobalt nitrate, zinc nitrate, thiourea and urea in a sufficient amount of 1: 9 volume ratio of absolute ethyl alcohol and deionized water, and reacting under strong stirring; repeatedly heating and cooling to 4 ℃ for at least three times, and removing precipitated biuret to obtain a salt solution;
and (3) putting 120ml of saline solution and 1.5g of the graphene PCL electrospun membrane composite material into a hydrothermal kettle, reacting for 18h at 205 ℃, and sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for 3 times to obtain the cobalt zinc sulfide/graphene nanoplatelets/PCL electrospun membrane composite material.
Example 3
A method for preparing a graphene/nanofiber/nanoparticle composite material, which is implemented by using the apparatus for preparing a graphene/nanofiber/nanoparticle composite material according to embodiment 1, the method comprising the following steps.
1) Preparing an electrospinning membrane: and (3) selecting a proper amount of PCL fiber, adding the PCL fiber into 100ml of analytically pure chloroform, and performing ultrasonic dispersion for 25min to obtain a PCL fiber chloroform dispersion liquid with the mass percent of 6%.
Selecting the electrospinning voltage of 12kV, the extrusion speed of 3.5ml/h, the receiving distance of 25cm, the electrospinning time of 2h and the ambient temperature of 5 ℃ to obtain the PCL electrospun membrane. Here, the voltage is as low as possible, the speed is as low as possible, and the ambient temperature is high, so that the electrospun membrane with the largest gap is expected to be obtained for preparation for subsequent use.
2) A film clamping step: selecting the obtained PCL electrospun membrane with the area larger than that of the upper pressing ring (2) or the lower pressing ring (5), sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for 4 times, completely airing, tensioning and clamping the cleaned PCL electrospun membrane between the upper pressing ring rubber 1 and the lower pressing ring rubber 4 to ensure that the PCL electrospun membrane is free of wrinkles.
3) Preparing a graphene nanoplatelet dispersion liquid: a large number of prefabricated expanded graphite sheet layers are used as raw materials, and graphene nanoplatelets are generated through ultrasonic stripping for more than 1h in absolute ethyl alcohol. Supplementing the solvent absolute ethyl alcohol of the graphene nanoplatelets to more than 200ml, carrying out high-intensity ultrasonic oscillation for 4min, immediately discarding half of the upper dispersion liquid, and repeating the above process for at least 8 times until the average radial size of the graphene nanoplatelets is higher than 8 um.
4) A negative pressure attaching step: conducting ultrasonic dispersion on 140ml of chloroform dispersion liquid containing 5-10% of graphene nanoplatelets with the average radial dimension higher than 5-10um by mass for 2min, introducing the chloroform dispersion liquid into the upper cylinder 3 at a very slow speed, after pouring, pumping the air pump for 5s at the flow rate of 1.2L/min, and stopping circulating repeatedly for 8s until no obvious liquid dripping of the PCL electrospun membrane is observed through the lower cylinder; a waste liquid cylinder is used for receiving and recycling the liquid flowing out from the lower liquid pipe (13); repeating the previous part of the operation of the step (4) for 15 times; cutting off a circular part attached by the graphene from the electrospun membrane attached with the graphene nanoplatelets, sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for at least 1 time, and completely airing to obtain the graphene PCL electrospun membrane composite material;
5) micro-carbonization: flattening the graphene PCL electrospun membrane composite material in a heating container, and micro-carbonizing for 90min at 220 ℃;
6) a hydrothermal reaction step: 6) dissolving cobalt nitrate, zinc nitrate, thiourea and urea in a sufficient amount of 1: 9 volume ratio of absolute ethyl alcohol and deionized water, and reacting under strong stirring; repeatedly heating and cooling to 4 ℃ for at least three times, and removing precipitated biuret to obtain a salt solution;
putting 140ml of saline solution and 2.5g of the graphene PCL electrospun membrane composite material into a hydrothermal kettle, reacting for 22h at 215 ℃, and sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for 5 times to obtain the cobalt zinc sulfide/graphene microchip/PCL electrospun membrane composite material.
Example 4
The cobalt zinc sulfide/graphene microchip/PCL electrospun membrane composite material is prepared by a preparation method of a composite material of graphene, nano fibers and nano particles, and is characterized in that: based on a partially carbonized PCL electrospun membrane, graphene micro-sheets with the average radial size higher than 5-10um are dispersed among PCL fibers, cobalt zinc sulfide nano-particles are also dispersed among the PCL fibers, the mass percentage of the graphene micro-sheets in the composite material is more than 3%, specifically 4/5/6/7%, and the mass percentage of the cobalt zinc sulfide nano-particles in the composite material is more than 5%, specifically 6/7/8/9%.
We have conducted some simple experiments to confirm the structural effect, wherein with the same area of PCL electrospun membrane, we compared the product added with graphene in electrospinning with the negative pressure attached graphene of the present application, the weight per unit area is increased by at least 1.2% and can reach up to about 2.3%, which fully embodies the better additional effect of graphene, comparing the composite material finally obtained in the present application with the material obtained in the aforementioned patent document, the BET adsorption value per unit mass indicates that the increase of the surface area is at least 60% or more. Taking catalytic gas as an example, the composite material has better technical effect in catalysis.
The basic idea of the invention is that after entering a carrier, a larger graphene microchip is subjected to micro-carbonization, so that a better condition is provided for subsequent nanoparticle dispersion, but the larger graphene microchip is not enough to be screened out by a light, and how to effectively enter PCL electrospun membranes as much as possible, the invention provides a meaningful way, and the prior art does not disclose or suggest.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (4)
1. A preparation method of a composite material of graphene, nano-fibers and nano-particles is implemented by using a preparation device of the composite material of graphene, nano-fibers and nano-particles, and is characterized in that the preparation device comprises the following steps:
the device comprises an upper barrel (3), an upper pressing ring (2), upper pressing ring rubber (1), lower pressing ring rubber (4), a lower pressing ring (5), a lower barrel (6), a bottom plate (7), an air outlet (8), an air outlet pipe (9), a buffer ball (12), a lower liquid pipe (13), an air exhaust pipe (10) and an air extractor (11);
the upper cylinder body is positioned on the upper pressure ring, the bottommost part of the upper cylinder body is provided with an upper flange, the innermost side of the upper pressure ring is provided with an upper groove matched with the upper flange, and the upper cylinder body and the upper pressure ring are tightly matched with each other through the upper flange and the upper groove;
the upper pressure ring rubber (1) is positioned on the lower surface of the upper pressure ring and is in a circular ring shape, the lower pressure ring rubber (4) is positioned on the upper surface of the lower pressure ring and is in a circular ring shape, the upper pressure ring rubber (1) and the lower pressure ring rubber (4) are uniform thin layers with the thickness of 600-1000 microns, the upper pressure ring rubber (1) is adhered to the lower surface of the upper pressure ring by glue, and the lower pressure ring rubber (4) is adhered to the upper surface of the lower pressure ring;
the upper pressure ring rubber (1) and the lower pressure ring rubber (4) are completely overlapped in projection in the overlooking direction, and a completely flattened PCL electrospun membrane is clamped between the upper pressure ring rubber and the lower pressure ring rubber;
the lower cylinder body is positioned below the lower pressure ring, the uppermost part of the lower cylinder body is provided with a circle of lower grooves, the innermost side of the lower pressure ring is provided with a lower flange matched with the lower grooves, the lower cylinder body and the lower pressure ring are tightly matched with each other through the lower flange and the lower grooves, the length of the lower flange in the Z-axis direction is at least 1cm, and the lower grooves have the depth matched with the lower flange;
the bottom plate (7) and the lower barrel (6) are integrally formed or are matched with each other to be tightly connected, and sealant is coated at the joint;
the air outlet (8) is vertical to the side wall of the lower cylinder body (6), and the distance between the central axis of the air outlet and the bottom plate (7) is not more than 10 cm;
the air extractor (11) is provided with a display panel and is used for displaying whether the air extractor is started or not at present and the flow of the extracted air;
the upper cylinder body (3), the upper pressure ring (2), the lower pressure ring (5), the lower cylinder body (6), the bottom plate (7) and the air outlet (8) are made of transparent or semitransparent hard polymeric materials; the air outlet pipe (9), the buffer ball (12), the liquid outlet pipe (13) and the air exhaust pipe (10) are made of transparent or semitransparent materials;
an anti-backflow sheet is arranged in the middle of the liquid discharging pipe (13), and the anti-backflow sheet can only be opened downwards;
the upper compression ring rubber (1) and the lower compression ring rubber (4) are made of scratch-resistant heat-vulcanized butyl rubber, and the surfaces of the upper compression ring rubber and the lower compression ring rubber are provided with uneven net-shaped lines;
the upper cylinder (3), the upper pressure ring (2), the lower pressure ring (5), the lower cylinder (6), the bottom plate (7), the air outlet (8) and the anti-backflow sheet are made of polypropylene or polycarbonate materials; the air outlet pipe (9), the buffer ball (12), the liquid outlet pipe (13) and the air exhaust pipe (10) are made of epoxy resin;
the air extractor is provided with a plurality of gears, the air extraction volume is between 0.5 and 5L/min, and the 12V direct current power supply is realized through alternating current conversion;
the preparation method comprises the following steps:
1) preparing an electrospinning membrane: selecting a proper amount of PCL fiber, adding into 100ml of analytically pure chloroform, and ultrasonically dispersing for 15-30min to obtain PCL fiber chloroform dispersion liquid with the mass percent of 3-7%;
selecting an electrospinning voltage of 10-15kV, an extrusion speed of 2-4ml/h, a receiving distance of 20-30cm, an electrospinning time of 2h and an ambient temperature of 4-8 ℃ to obtain a PCL electrospinning membrane;
2) a film clamping step: selecting the obtained PCL electrospun membrane with the area larger than that of the upper pressing ring (2) or the lower pressing ring (5), sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for at least 1 time, and after completely airing, tensioning and clamping the cleaned PCL electrospun membrane between the upper pressing ring rubber (1) and the lower pressing ring rubber (4) to ensure that the PCL electrospun membrane is not wrinkled;
3) preparing a graphene nanoplatelet dispersion liquid: taking a large number of prefabricated expanded graphite sheet layers as raw materials, and ultrasonically stripping in absolute ethyl alcohol for more than 1h to generate graphene nanoplatelets;
supplementing the solvent absolute ethyl alcohol of the graphene nanoplatelets to more than 200ml, carrying out high-intensity ultrasonic oscillation for 3-5min, immediately discarding the upper half of dispersion liquid, and repeating the above process for at least 5 times until the average radial size of the graphene nanoplatelets is higher than 5-10 mu m;
4) a negative pressure attaching step: conducting ultrasonic dispersion on 150ml of chloroform dispersion liquid containing 5-10% of graphene micro-sheets with the average radial dimension of more than 5-10 mu m by mass percent for 1-2min, introducing the chloroform dispersion liquid into the upper cylinder (3) at a very slow speed, after pouring, pumping the air pump for 2-5s at the flow rate of 0.5-1.5L/min, and stopping circulating for 5-8s repeatedly until no obvious liquid dripping of the PCL electrospun membrane is observed through the lower cylinder; a waste liquid cylinder is used for receiving and recycling the liquid flowing out from the lower liquid pipe (13);
repeating the process from ultrasonic dispersion to recovery for 10-20 times;
cutting off a circular part attached by the graphene from the electrospun membrane attached with the graphene nanoplatelets, sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for at least 1 time, and completely airing to obtain the graphene PCL electrospun membrane composite material;
5) micro-carbonization: placing the graphene PCL electrospun membrane composite material in a heating container, leveling, and carrying out micro-carbonization for 30-90min at the temperature of 210-225 ℃;
6) a hydrothermal reaction step: dissolving cobalt nitrate, zinc nitrate, thiourea and urea in a sufficient amount of 1: 9 volume ratio of absolute ethyl alcohol and deionized water, and reacting under strong stirring; repeatedly heating and cooling to 4 ℃ for at least three times, and removing precipitated biuret to obtain a salt solution;
and (3) putting 100-150ml of saline solution and 1-3g of the PCL electrospun membrane composite material into a hydrothermal kettle, reacting for 16-24h at the temperature of 200-220 ℃, and sequentially using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol to respectively clean the silicon wafer for 3-5 times to obtain the cobalt zinc sulfide/graphene nanoplatelets/PCL electrospun membrane composite material.
2. The method of claim 1, wherein the graphene/nanofiber/nanoparticle composite material comprises:
in the step 1, performing ultrasonic dispersion for 20min to obtain a PCL fiber chloroform dispersion liquid with the mass percent of 5%; selecting an electrospinning voltage of 10kV, an extrusion speed of 2.5ml/h, a receiving distance of 20cm, an electrospinning time of 2h and an ambient temperature of 4 ℃;
in the step 2, the silicon wafer is respectively washed for 3 times by using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol in sequence;
in the step 3, carrying out high-intensity ultrasonic oscillation for 3min, immediately discarding half of the dispersion liquid on the upper layer, and repeating the process for at least 5 times until the average radial size of the graphene nanoplatelets is higher than 5 microns;
in the step 4, performing ultrasonic dispersion on 120ml of 6% chloroform dispersion liquid for 1min, introducing the chloroform dispersion liquid into the upper cylinder (3) at a very slow speed, and after pouring is finished, pumping the chloroform dispersion liquid for 3s at a flow rate of 0.6L/min by using the air pump, and then stopping circulation for 6 s;
in step 5, micro-carbonizing at 210 ℃ for 50 min;
in step 6, 120ml of saline solution and 1.5g of the graphene PCL electrospun membrane composite material are placed in a hydrothermal kettle, the reaction is carried out for 18 hours at 205 ℃, and the silicon wafer is washed for 3 times by using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol in sequence.
3. The method of claim 1, wherein the graphene/nanofiber/nanoparticle composite material comprises:
in the step 1, performing ultrasonic dispersion for 25min to obtain PCL fiber chloroform dispersion liquid with the mass percent of 6%; selecting an electrospinning voltage of 12kV, an extrusion speed of 3.5ml/h, a receiving distance of 25cm, an electrospinning time of 2h and an ambient temperature of 5 ℃;
in the step 2, the silicon wafer is respectively washed for 4 times by using sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol in sequence;
in the step 3, carrying out high-intensity ultrasonic oscillation for 4min, immediately discarding half of the dispersion liquid on the upper layer, and repeating the process for at least 8 times until the average radial size of the graphene nanoplatelets is higher than 8 μm;
in the step 4, 140ml of 6% chloroform dispersion liquid is ultrasonically dispersed for 2min, is guided into the upper cylinder (3) at a very slow speed, and is repeatedly circulated in a mode that the air extractor sucks the chloroform dispersion liquid for 5s at a flow rate of 1.2L/min after pouring is finished and then stops for 8 s;
in step 5, micro-carbonizing at 210 ℃ for 50 min;
in step 6, 140ml of saline solution and 2.5g of the graphene PCL electrospun membrane composite material are placed in a hydrothermal kettle, the mixture reacts for 22 hours at 215 ℃, and sufficient tetrahydrofuran, absolute ethyl alcohol, double distilled water and absolute ethyl alcohol are sequentially used for cleaning the silicon wafer for 5 times.
4. A cobalt zinc sulfide/graphene micro-sheet/PCL electrospun membrane composite material prepared by the preparation method of the composite material of graphene, nano-fibers and nano-particles according to claim 1, which is characterized in that:
based on a PCL electrospun membrane after partial carbonization, graphene micro-sheets with the average radial size higher than 5-10 mu m are dispersed among PCL fibers, cobalt zinc sulfide nano-particles are also dispersed among the PCL fibers, the mass percentage of the graphene micro-sheets in the composite material is more than 3%, and the mass percentage of the cobalt zinc sulfide nano-particles in the composite material is more than 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811419793.5A CN109529635B (en) | 2018-11-26 | 2018-11-26 | Composite material of graphene, nano-fiber and nano-particle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811419793.5A CN109529635B (en) | 2018-11-26 | 2018-11-26 | Composite material of graphene, nano-fiber and nano-particle and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109529635A CN109529635A (en) | 2019-03-29 |
| CN109529635B true CN109529635B (en) | 2021-11-09 |
Family
ID=65849786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811419793.5A Active CN109529635B (en) | 2018-11-26 | 2018-11-26 | Composite material of graphene, nano-fiber and nano-particle and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109529635B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110779189A (en) * | 2019-11-06 | 2020-02-11 | 深圳市前海大众鑫环保科技有限公司 | Fresh air purification system composed of air conditioner and graphene nanofiber membrane total heat exchanger |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0205970B1 (en) * | 1985-05-30 | 1990-10-24 | Research Development Corporation of Japan | Process for producing graphite films |
| CN105297405A (en) * | 2015-10-25 | 2016-02-03 | 复旦大学 | Cobalt zinc sulfide/graphene/carbon nanofiber composite material and preparing method thereof |
| CN106964262A (en) * | 2017-04-13 | 2017-07-21 | 东华大学 | A kind of nanofiber-based osmosis vaporizing compound membrane and preparation method thereof |
| CN108589268A (en) * | 2018-04-13 | 2018-09-28 | 西安交通大学 | A kind of conductive-nano-fibers material and preparation method |
-
2018
- 2018-11-26 CN CN201811419793.5A patent/CN109529635B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0205970B1 (en) * | 1985-05-30 | 1990-10-24 | Research Development Corporation of Japan | Process for producing graphite films |
| CN105297405A (en) * | 2015-10-25 | 2016-02-03 | 复旦大学 | Cobalt zinc sulfide/graphene/carbon nanofiber composite material and preparing method thereof |
| CN106964262A (en) * | 2017-04-13 | 2017-07-21 | 东华大学 | A kind of nanofiber-based osmosis vaporizing compound membrane and preparation method thereof |
| CN108589268A (en) * | 2018-04-13 | 2018-09-28 | 西安交通大学 | A kind of conductive-nano-fibers material and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109529635A (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | A coupled photo-piezo-catalytic effect in a BST-PDMS porous foam for enhanced dye wastewater degradation | |
| CN109341902B (en) | Flexible pressure sensor with graphene as electrode material and preparation method thereof | |
| Jia et al. | Flexible ceramic fibers: Recent development in preparation and application | |
| CN110164716B (en) | Preparation method of thin film electrode based on covalent organic framework material | |
| CN107069050B (en) | A kind of porous carbon nanotube and preparation method thereof of Co/N/S doping | |
| CN106654126A (en) | Lithium-sulfur battery separator and preparation method thereof | |
| CN108940285A (en) | A kind of preparation method and application of flexibility electrolysis water catalysis material | |
| CN107034663B (en) | A kind of tungsten disulfide/carbon nano-fiber composite material and its preparation method and application | |
| CN1803594A (en) | Large-area ultra-thin carbon nanotube film and its preparation process | |
| CN102877218B (en) | A kind of preparation method of hydrophobic oil suction silicon carbide ceramic fiber felt | |
| CN104495796B (en) | The method preparing porous class grapheme material for raw material with Herba Eichhorniae | |
| CN106409525B (en) | Graphene, conducting fibre composite material and its with the preparation method of multi-stage porous carbon composite material, its product and application | |
| CN110130098A (en) | A kind of super-hydrophobic hydrotalcite composite membrane and preparation method thereof | |
| CN107934955A (en) | A kind of method of activation process commercialization carbon cloth | |
| CN109592962A (en) | A kind of bionical ternary system graphene-black phosphorus nanocomposite films preparation method | |
| CN109529635B (en) | Composite material of graphene, nano-fiber and nano-particle and preparation method thereof | |
| CN108149343A (en) | The composite nano fiber of N doping porous carbon cladding nano silicon particles and preparation | |
| CN109179385B (en) | Multi-channel graphene film and preparation method thereof | |
| CN112646212B (en) | Preparation method of polyaniline-coated metal organic framework nano-array film, product and application thereof | |
| CN1843905A (en) | Method for preparing composite material of carbon nanotube with electric field for controlling arrangement thereof | |
| CN111925776B (en) | Preparation method of polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material | |
| CN111389439A (en) | Preparation method of BN quantum dot combined photocatalytic composite fiber | |
| CN107321383A (en) | A kind of nano-fibre supported cobalt silver alloy and its preparation method and application | |
| CN112724560A (en) | Piezoelectric film for road surface power generation and preparation method thereof | |
| CN113083272A (en) | FeNxPreparation method of nano-particle doped bamboo-like carbon nano-tube |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20230329 Granted publication date: 20211109 |