CN109529635A - The composite material and preparation method of graphene and nanofiber and nano particle - Google Patents
The composite material and preparation method of graphene and nanofiber and nano particle Download PDFInfo
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- CN109529635A CN109529635A CN201811419793.5A CN201811419793A CN109529635A CN 109529635 A CN109529635 A CN 109529635A CN 201811419793 A CN201811419793 A CN 201811419793A CN 109529635 A CN109529635 A CN 109529635A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- 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
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- 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
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- 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
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- 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
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- 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
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
A kind of preparation facilities of graphene and nanofiber and the composite material of nano particle, including upper shell (3), upper press ring (2), upper press ring rubber (1), lower pressure ring rubber (4), lower pressure ring (5), lower shell (6), bottom plate (7), gas outlet (8), escape pipe (9), buffering ball (12), lower liquid pipe (13), exhaust tube (10), air exhauster (11).It further include the composite material prepared using the preparation facilities, and the method using the preparation facilities.
Description
Technical field
The present invention relates to graphene composite material technical field, specially a kind of graphene and nanofiber and nano particle
Composite material and preparation method, device.
Background technique
Graphene is a kind of two-dimensional material of only one atomic thickness being made of carbon atom, has very excellent object
Physicochemical performance, such as excellent mechanical property, high electric conductivity and good heating conduction, it is considered to be most latent now
One of nano material of power.As a kind of one-dimensional carbon nano material, carbon nano-fiber has good mechanical property, biggish ratio
The advantages that surface area and good chemical stability, these special natures make that it is widely used in catalyst carrier, macromolecule is received
The fields such as the flexible base material of nano composite material, energy conversion and memory device.By taking graphene microchip as an example, not only itself
Have a preferable physical property performance, electric property, and with the compound performance that can further promote other materials of other materials.
Electrostatic spinning is technology that is a kind of simple and effectively preparing carbon nano-fiber, by high-pressure electrostatic by polymer solution
Spinning is carried out, then carry out pre-oxidation and high temperature cabonization the Static Spinning with three-dimensional porous structure and high-specific surface area can be prepared
Carbon nanofiber membrane.This patent uses electrostatic spinning process, polyacrylonitrile solution is carried out spinning, and be prepared by pre-oxidation
To polyacrylonitrile nanofiber film.
Document CN105297405A describes complex method, wraps on polyacrylonitrile nanofiber by solution infusion method
Wrap up in graphene oxide, then graphene/carbon nano-fiber composite film be prepared by high temperature cabonization, and as base material into
One step prepares high-performance composite materials.This method has obvious shortcoming, first is that high temperature, second is that the mode that graphene is added is too simple,
Additional amount is insufficient, and compound situation is also uneven, it is difficult to be the evenly dispersed carrier provided of cobalt sulfide zinc nanoparticles.
Cobalt sulfide zinc is a kind of typical metal sulfide, and self-conductive is good, and theoretical capacity value is high.With general material phase
Than cobalt sulfide zinc has very high electric conductivity and theoretical lithium storage content value, in catalysis, supercapacitor and lithium ion battery battery
It is widely paid close attention to and is applied in the fields such as pole material.Pure cobalt sulfide zinc particle is easy to reunite, this is to restrict its application most
Big problem makes its active site be unable to get abundant exposure, has seriously affected the stable circulation of its catalysis characteristics and energy stores
Property, serious material of reuniting is prepared, superior function can not embody.Therefore, receiving cobalt sulfide zinc and excellent in stability
Rice material progress is effectively compound, sufficiently improves the stability of cobalt sulfide zinc, is of great significance to it.
The dispersed sulfur cobalt zinc for how effectively, effectively dispersed graphite alkene in the porous material, with play promote it is equal
Even attachment is a kind of effective means, but has obvious deficiency in above-mentioned CN105297405A, first is that graphene only with
Immersion way attachment, the size for the graphene how to adhere to, uniformity have very big problem, are difficult to play to the attached of cobalt sulfide zinc
Play the role of good, and its carbonization mode temperature used is too high, is carbonized at a temperature of so high, actually right
In fibre structure integrality influence it is very big, actually will appear many biggish cavities, for cobalt sulfide zinc dispersion and
Uniformly attachment is totally unfavorable;" method of electrostatic spinning prepares polycaprolactone/graphene composite material and receives the document of Chinese University of Science and Technology's journal
Rice fiber " a kind of method of dispersed graphite alkene in electrospinning film is provided, but be constrained to add graphene, stone in electrospinning liquid
The concentration of black alkene at most only has 1% or so, and from the electromicroscopic photograph in text, just adds graphene to fibre in electrospinning link
Tieing up structure influences greatly, and great irregularity occurs in fibre structure, and such structure is evenly dispersed for cobalt sulfide zinc
Deficiency is benefited, it can not be as good carrier.
In the prior art, research and analysis are not carried out for how preparing the good carrier of cobalt sulfide zinc, and cobalt sulfide
The performance of zinc is difficult to embody due to the deficiency of dispersion degree.
Summary of the invention
The purpose of the present invention is to provide a kind of good composite materials, to solve the cobalt sulfide zinc performance of existing technology
Still there is limitation, the dispersion degree that disperses in porous carrier is insufficient, and superperformance is had no way of the defect played.Relative to existing skill
Art, the present invention adhere to the graphene microchip of specific dimensions by negative pressure effective in PCL electrospinning film, then carry out the micro- carbonization of low temperature,
Effectively excellent carrier is provided for the dispersion of cobalt sulfide zinc.
To achieve the above object, the invention provides the following technical scheme: a kind of graphene and nanofiber and nano particle
Composite material preparation facilities, comprising: upper shell, upper press ring, upper press ring rubber, lower pressure ring rubber, lower pressure ring, lower shell,
Bottom plate, gas outlet, escape pipe, buffering ball, lower liquid pipe, exhaust tube, air exhauster.Above-mentioned upper shell is located on upper press ring, upper cylinder
Body bottom has a circle upper flange, and upper press ring most inner side has the upper groove matched with upper flange, upper shell and upper press ring
It is fitted close by upper flange and upper groove;The upper press ring rubber is located at upper press ring lower surface and annular in shape, the pushing
Ring rubber is located at lower pressure ring upper surface and annular in shape, and the upper press ring rubber and lower pressure ring rubber are thickness in 600um-
Thin uniform layer between 1000um, blend compounds by the upper press ring rubber adhesion in upper press ring lower surface, by the lower pressure ring rubber
Glue bond is in lower pressure ring upper surface.
The upper press ring rubber and lower pressure ring rubber are completely coincident in overlook direction projection, are clamped with therebetween completely
The PCL electrospinning film of flattening.
Above-mentioned lower shell is located under lower pressure ring, and lower shell the top has a circle lower groove, and lower pressure ring most inner side has
The lower flange matched with lower groove, lower shell and lower pressure ring are fitted close by lower flange and lower groove, and the lower flange is in Z
The length of axis direction is at least 1-2cm, and the lower groove has the depth to match therewith.
The bottom plate and lower shell are integrally formed, or the close connection that cooperates, and are coated in junction close
Sealing;Perpendicular to lower shell side wall, center axis thereof is not more than 10cm with a distance from bottom plate for the gas outlet;The air exhauster has
Display panel, whether for showing current open and the flow of gas bleeding.
The upper shell, upper press ring, lower pressure ring, lower shell, bottom plate, gas outlet material be transparent or semitransparent hard
Polymeric material;The escape pipe, buffering ball, lower liquid pipe, the material of exhaust tube are transparent or semitransparent;The middle part of the lower liquid pipe
Equipped with counnter attack flow, which can only be opened downwards.
Further: the upper press ring rubber, lower pressure ring rubber material be the heat cure butyl rubber of scratch-resistant, and table
Face has rough netted lines;The upper shell, upper press ring, lower pressure ring, lower shell, bottom plate, gas outlet, counnter attack flow
Material be polypropylene or makrolon material;The escape pipe, buffering ball, lower liquid pipe, the material of exhaust tube are asphalt mixtures modified by epoxy resin
Rouge;The air exhauster has several gears, is evacuated air quantity between 0.5-5L/min, is supplied by the 12V DC electricity that alternating current is converted
Electricity.
A kind of preparation method of graphene and nanofiber and the composite material of nano particle, utilizes foregoing one
Kind graphene is with the preparation facilities of nanofiber and the composite material of nano particle to implement, which is characterized in that including following step
It is rapid:
1) electrospinning film preparation step: choosing appropriate PCL fiber and be added among the pure chloroform of 100ml analysis, ultrasonic disperse 15-
30min obtains mass percent in the PCL fiber chloroform dispersion liquid of 3-7%.
Electrospinning voltages 10-15kV, extruded velocity 2-4ml/h are chosen, distance 20-30cm is received, 2h, environment between when electrospinning
Temperature is 4-8 DEG C, obtains PCL electrospinning film.
2) film gripping step: the PCL electrospinning film greater than upper press ring (2) or lower pressure ring (5) area chosen successively makes
It is respectively washed silicon wafer at least 1 time with enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol, it, will be clear after drying completely
PCL electrospinning film after washing is tensed and is clamped between upper press ring rubber (1) and lower pressure ring rubber (4), its corrugationless is made.
3) graphene microchip dispersion solution preparing step: using prefabricated a large amount of expanded graphite lamellas as raw material, in dehydrated alcohol
The middle ultrasound removing through 1h or more generates graphene microchip.
The solvent absolute ethyl alcohol of graphene microchip is supplemented to 200ml or more, high strength supersonic shakes 3-5min, abandons at once
The dispersion liquid of upper layer half is removed, is repeated above procedure at least 5-10 times, until the average radial size of graphene microchip is higher than 5-
10um。
4) the graphene microchip mass percent of 5-10um negative pressure attachment steps: will be higher than containing aforementioned average radial size
Chloroform dispersion liquid 100-150ml between 5-10% is imported in upper shell (3) through 1-2min ultrasonic disperse with pole jogging speed,
After toppling over and finishing, the air exhauster is followed repeatedly in a manner of stopping 5-8s after 0.5-1.5L/min flow rate aspirates 2-5s
Ring, until observing that PCL electrospinning film drips without obvious liquid through lower shell;The liquid of lower liquid pipe (13) outflow is received with waste liquid cylinder
Body simultaneously recycles;Step (4) preceding sections are repeated to operate 10-20 times;Electrospinning film after attachment graphene microchip is cut by graphite
The circular portion of alkene attachment, is successively respectively washed silicon wafer using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol
It at least 1 time, dries completely, obtains graphene PCL electrospinning film composite material.
5) micro- carburising step: graphene PCL electrospinning film composite material is put and is evened up in the heating container, at 210-225 DEG C
Under micro- carbonization 30-90min.
6) hydro-thermal reaction step: 6) cobalt nitrate, zinc nitrate, thiocarbamide and urea according to the quality proportioning of 2:1:2:4 are dissolved in
In the mixed liquor of the dehydrated alcohol deionized water of enough 1:9 volume ratios, the lower reaction of strong stirring;4 DEG C are heated-are cooled to repeatedly extremely
Less three times, the biuret of precipitation is removed, salting liquid is obtained.
The salting liquid of 100-150ml and 1-3g graphene PCL electrospinning film composite material are put into water heating kettle, 200-220
16-24h is reacted at DEG C, is successively respectively washed silicon wafer 3-5 using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol
It is secondary, obtain cobalt sulfide zinc/graphene microchip/PCL electrospinning film composite material.
A kind of cobalt sulfide zinc/graphene microchip/PCL electrospinning film composite material uses a kind of foregoing graphene
It is prepared with the preparation method of nanofiber and the composite material of nano particle, which is characterized in that attribute are as follows: with a kind of part
Based on PCL electrospinning film after carbonization, it is micro- higher than the graphene of 5-10um that average radial size is dispersed between PCL fiber
Piece is also dispersed with cobalt sulfide zinc nanoparticles between PCL fiber, and it is big that the graphene microchip accounts for composite material mass percent
In 3%, the cobalt sulfide zinc nanoparticles account for composite material mass percent greater than 5%.
Compared with prior art, the invention has the following advantages: 1) effective load of graphene, compares more existing skill
In art, the present invention innovatively in the way of negative-pressure adsorption, is effectively loaded with the bigger graphene microchip of radial dimension, leads to
It crosses very low negative pressure reverse and relapses attachment, so that absorption is highly effective, provide condition, the prior art for the preparation of good carrier
Do not enlighten.2) high temperature cabonization is not taken but micro- carbonization, PCL fiber will be carbonized at 150 DEG C or more here, still
It is just greatly accelerated in 225 degrees Celsius or more carbonisations, but height carbonization, high temperature cabonization are very not for the attachment of carrier
Benefit, the temperature of non-high-speed carbonation stage is used here, so that only micro- carbonization in carrier, does not have big damage in structure,
Conducive to subsequent attachment.3) graphene that such method introduces not only is measured greatly, but also uniformly, but also the adhesion amount of cobalt sulfide zinc is big
It is big to increase, increased on year-on-year basis in the amount of the cobalt sulfide zinc of inner surface of the carrier attachment it is very much, the prior art there is no open or
Enlightenment.
Detailed description of the invention
Fig. 1 is apparatus of the present invention texture edge schematic cross-sectional view.
In figure: 1, upper press ring rubber, 2, upper press ring, 3, upper shell, 4, lower pressure ring rubber, 5, lower pressure ring, 6, lower shell, 7,
Bottom plate, 8, gas outlet, 9, escape pipe, 10, exhaust tube, 11, air exhauster, 12, buffering ball, 13, lower liquid pipe.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation facilities of graphene and nanofiber and the composite material of nano particle, comprising: upper shell 3, upper pressure
Ring 2, upper press ring rubber 1, lower pressure ring rubber 4, lower pressure ring 5, lower shell 6, bottom plate 7, gas outlet 8, escape pipe 9, buffering ball 12, under
Liquid pipe 13, exhaust tube 10, air exhauster 11;Above-mentioned upper shell is located on upper press ring, and upper shell bottom has a circle upper flange,
There is upper press ring most inner side the upper groove matched with upper flange, upper shell and upper press ring closely to be matched by upper flange and upper groove
It closes;The upper press ring rubber 1 is located at upper press ring lower surface and annular in shape, and the lower pressure ring rubber 4 is located at lower pressure ring upper surface
And it is annular in shape, the upper press ring rubber 1 and lower pressure ring rubber 4 are thickness in 600um/700um/800um/900um/1000um
Thin uniform layer, the upper press ring rubber 1 is bonded in upper press ring lower surface, the lower pressure ring rubber 4 is bonded in by blend compounds
Lower pressure ring upper surface;The upper press ring rubber 1 and lower pressure ring rubber 4 are completely coincident in overlook direction projection, are pressed from both sides therebetween
Hold the PCL electrospinning film flattened completely;Above-mentioned lower shell is located under lower pressure ring, and lower shell the top has a circle lower groove,
There is lower pressure ring most inner side the lower flange matched with lower groove, lower shell and lower pressure ring closely to be matched by lower flange and lower groove
It closes, the lower flange is at least 1-2cm in the length of Z-direction, and the lower groove has the depth to match therewith;The bottom plate
7 and lower shell 6 be integrally formed, or the close connection that cooperates, and be coated with sealant, the sealant in junction
It is 3M glue or polyurethane base rubber;The gas outlet 8 is not more than with a distance from bottom plate 7 perpendicular to 6 side wall of lower shell, center axis thereof
10cm, e.g. 7/8/9cm;The air exhauster 11 has display panel, whether for showing current open and gas bleeding
Flow;The upper shell 3, upper press ring 2, lower pressure ring 5, lower shell 6, bottom plate 7, gas outlet 8 material be it is transparent or semitransparent
Rigid polymeric material;The escape pipe 9, buffering ball 12, lower liquid pipe 13, the material of exhaust tube 10 are transparent or semitransparent;Institute
The middle part for stating lower liquid pipe 13 is equipped with counnter attack flow, which can only open downwards.
The upper press ring rubber 1, lower pressure ring rubber 4 material be scratch-resistant heat cure butyl rubber, surface is through really up to the mark
Change processing, and surface has rough netted lines, there is certain skin-friction force;The upper shell 3, upper press ring 2, under
Pressure ring 5, lower shell 6, bottom plate 7, gas outlet 8, counnter attack flow material be polypropylene or makrolon material, transparency is with energy
Enough see that internal flow situation is advisable;The escape pipe 9, buffering ball 12, lower liquid pipe 13, the material of exhaust tube 10 are asphalt mixtures modified by epoxy resin
Rouge, epoxy resin here are that toughness is stronger, are difficult to happen plastic deformation under conventional use;The air exhauster has several gears,
Air quantity is evacuated between 0.5-5L/min, such as 0.5,1,1.5,2,2.5,3,3.5,4, the 12V DC electricity converted by alternating current
Power supply.External power supply is 110 or 220V.
Embodiment 2
A kind of preparation method of graphene and nanofiber and the composite material of nano particle, using such as 1 institute of embodiment
A kind of graphene stated is with the preparation facilities of nanofiber and the composite material of nano particle to implement, which is characterized in that including
Following steps.
1) electrospinning film preparation step: choosing appropriate PCL fiber and be added among the pure chloroform of 100ml analysis, ultrasonic disperse
20min obtains PCL fiber chloroform dispersion liquid of the mass percent 5%.
Electrospinning voltages 10kV, extruded velocity 2.5ml/h are chosen, distance 20cm, electrospinning time 2h, environment temperature 4 are received
DEG C, obtain PCL electrospinning film.Here voltage is low as far as possible, and speed is slow as far as possible, and environment temperature is high, is that expectation obtains gap as far as possible greatly
Electrospinning film, prepare to be subsequent.
2) film gripping step: the PCL electrospinning film greater than upper press ring (2) or lower pressure ring (5) area chosen successively makes
It is respectively washed silicon wafer 3 times with enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol, after drying completely, after cleaning
PCL electrospinning film tense and be clamped between upper press ring rubber 1 and lower pressure ring rubber 4, make its corrugationless.
3) graphene microchip dispersion solution preparing step: using prefabricated a large amount of expanded graphite lamellas as raw material, in dehydrated alcohol
The middle ultrasound removing through 1h or more generates graphene microchip.The solvent absolute ethyl alcohol of graphene microchip is supplemented to 200ml or more,
High strength supersonic shakes 3min, discards the dispersion liquid of upper layer half at once, repeats above procedure at least 5 times, until graphene is micro-
The average radial size of piece is higher than 5um.
4) the graphene microchip mass percent of 5-10um negative pressure attachment steps: will be higher than containing aforementioned average radial size
Chloroform dispersion liquid 120ml between 5-10% is imported in upper shell 3 with pole jogging speed, is being toppled over through 1min ultrasonic disperse
Finish after, by the air exhauster by 0.6L/min flow rate aspirate 3s after stop 6s in a manner of iterative cycles, until penetrate lower shell
Observe that PCL electrospinning film drips without obvious liquid;The liquid and recycling of lower liquid pipe (13) outflow are received with waste liquid cylinder;Repeat step
(4) preceding sections operate 15 times;Electrospinning film after attachment graphene microchip is cut into the circular portion adhered to by graphene, successively
It is respectively washed silicon wafer at least 1 time using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol, dries, obtain completely
Graphene PCL electrospinning film composite material;
5) micro- carburising step: graphene PCL electrospinning film composite material being put and is evened up in the heating container, micro- at 210 DEG C
Be carbonized 50min;
6) hydro-thermal reaction step: 6) cobalt nitrate, zinc nitrate, thiocarbamide and urea according to the quality proportioning of 2:1:2:4 are dissolved in
In the mixed liquor of the dehydrated alcohol deionized water of enough 1:9 volume ratios, the lower reaction of strong stirring;4 DEG C are heated-are cooled to repeatedly extremely
Less three times, the biuret of precipitation is removed, salting liquid is obtained;
The salting liquid of 120ml and 1.5g graphene PCL electrospinning film composite material are put into water heating kettle, reacted at 205 DEG C
18h is successively respectively washed silicon wafer 3 times using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol, is vulcanized
Cobalt zinc/graphene microchip/PCL electrospinning film composite material.
Embodiment 3
A kind of preparation method of graphene and nanofiber and the composite material of nano particle, using such as 1 institute of embodiment
A kind of graphene stated is with the preparation facilities of nanofiber and the composite material of nano particle to implement, which is characterized in that including
Following steps.
1) electrospinning film preparation step: choosing appropriate PCL fiber and be added among the pure chloroform of 100ml analysis, ultrasonic disperse
25min obtains PCL fiber chloroform dispersion liquid of the mass percent 6%.
Electrospinning voltages 12kV, extruded velocity 3.5ml/h are chosen, distance 25cm, electrospinning time 2h, environment temperature 5 are received
DEG C, obtain PCL electrospinning film.Here voltage is low as far as possible, and speed is slow as far as possible, and environment temperature is high, is that expectation obtains gap as far as possible greatly
Electrospinning film, prepare to be subsequent.
2) film gripping step: the PCL electrospinning film greater than upper press ring (2) or lower pressure ring (5) area chosen successively makes
It is respectively washed silicon wafer 4 times with enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol, after drying completely, after cleaning
PCL electrospinning film tense and be clamped between upper press ring rubber 1 and lower pressure ring rubber 4, make its corrugationless.
3) graphene microchip dispersion solution preparing step: using prefabricated a large amount of expanded graphite lamellas as raw material, in dehydrated alcohol
The middle ultrasound removing through 1h or more generates graphene microchip.The solvent absolute ethyl alcohol of graphene microchip is supplemented to 200ml or more,
High strength supersonic shakes 4min, discards the dispersion liquid of upper layer half at once, repeats above procedure at least 8 times, until graphene is micro-
The average radial size of piece is higher than 8um.
4) the graphene microchip mass percent of 5-10um negative pressure attachment steps: will be higher than containing aforementioned average radial size
Chloroform dispersion liquid 140ml between 5-10% is imported in upper shell 3 with pole jogging speed, is being toppled over through 2min ultrasonic disperse
Finish after, by the air exhauster by 1.2L/min flow rate aspirate 5s after stop 8s in a manner of iterative cycles, until penetrate lower shell
Observe that PCL electrospinning film drips without obvious liquid;The liquid and recycling of lower liquid pipe (13) outflow are received with waste liquid cylinder;Repeat step
(4) preceding sections operate 15 times;Electrospinning film after attachment graphene microchip is cut into the circular portion adhered to by graphene, successively
It is respectively washed silicon wafer at least 1 time using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol, dries, obtain completely
Graphene PCL electrospinning film composite material;
5) micro- carburising step: graphene PCL electrospinning film composite material being put and is evened up in the heating container, micro- at 220 DEG C
Be carbonized 90min;
6) hydro-thermal reaction step: 6) cobalt nitrate, zinc nitrate, thiocarbamide and urea according to the quality proportioning of 2:1:2:4 are dissolved in
In the mixed liquor of the dehydrated alcohol deionized water of enough 1:9 volume ratios, the lower reaction of strong stirring;4 DEG C are heated-are cooled to repeatedly extremely
Less three times, the biuret of precipitation is removed, salting liquid is obtained;
The salting liquid of 140ml and 2.5g graphene PCL electrospinning film composite material are put into water heating kettle, reacted at 215 DEG C
22h is successively respectively washed silicon wafer 5 times using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol, is vulcanized
Cobalt zinc/graphene microchip/PCL electrospinning film composite material.
Embodiment 4
A kind of cobalt sulfide zinc/graphene microchip/PCL electrospinning film composite material uses a kind of graphite as claimed in claim 3
Prepared by the preparation method of alkene and nanofiber and the composite material of nano particle, it is characterised in that: with a kind of partially carbonized
Based on PCL electrospinning film afterwards, the graphene microchip that average radial size is higher than 5-10um is dispersed between PCL fiber,
Cobalt sulfide zinc nanoparticles are also dispersed between PCL fiber, the graphene microchip accounts for composite material mass percent and is greater than
3%, specially 4/5/6/7%, the cobalt sulfide zinc nanoparticles account for composite material mass percent greater than 5%, specially 6/
7/8/9。
We conducted some simple tests to confirm effect structure, wherein the PCL electrospinning film of same area, we will
The negative pressure attachment graphene of product and the application that graphene is added in electrospinning compares, and unit area at least weight increases
1.2% or more, highest can achieve 2.3% or so, fully demonstrate the better additional effect of graphene, and the application is final
The material that obtained composite material and aforementioned patent literature obtains compares, and the BET absorption numerical value of unit mass indicates, surface area
Increase at least 60% or more.By taking catalyzed gas as an example, such composite material necessarily leads to superior technique effect in catalysis
Fruit.
Basic ideas of the invention are, based on bigger graphene microchip after entering carrier, by micro- carbonization, meeting
There is provided preferable condition for the dispersion of subsequent nano particle, but light sift out big microplate be it is inadequate, how it to be allowed to have as far as possible
Effect ground enters between PCL electrospinning film, and the invention proposes a kind of significant mode, the prior art is not disclosed or enlightened.
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art,
It is still possible to modify the technical solutions described in the foregoing embodiments, or part of technical characteristic is carried out etc.
With replacement, all within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection scope of invention.
Claims (6)
1. a kind of preparation facilities of the composite material of graphene and nanofiber and nano particle, comprising:
Upper shell (3), upper press ring (2), upper press ring rubber (1), lower pressure ring rubber (4), lower pressure ring (5), lower shell (6), bottom plate
(7), gas outlet (8), escape pipe (9), buffering ball (12), lower liquid pipe (13), exhaust tube (10), air exhauster (11);
Above-mentioned upper shell is located on upper press ring, and upper shell bottom has a circle upper flange, upper press ring most inner side have with it is upper
The upper groove that flange matches, upper shell and upper press ring are fitted close by upper flange and upper groove;
The upper press ring rubber (1) is located at upper press ring lower surface and annular in shape, and the lower pressure ring rubber (4) is located on lower pressure ring
Surface is simultaneously annular in shape, and the upper press ring rubber (1) and lower pressure ring rubber (4) are that thickness is uniform between 600um-1000um
The upper press ring rubber (1) is bonded in upper press ring lower surface by thin layer, blend compounds, and the lower pressure ring rubber (4) is bonded in down
Pressure ring upper surface;
The upper press ring rubber (1) and lower pressure ring rubber (4) are completely coincident in overlook direction projection, have been clamped with therebetween
The PCL electrospinning film flattened entirely;
Above-mentioned lower shell is located under lower pressure ring, and lower shell the top has a circle lower groove, and lower pressure ring most inner side has under
The lower flange that groove matches, lower shell and lower pressure ring are fitted close by lower flange and lower groove, and the lower flange is in Z axis side
To length be at least 1-2cm, the lower groove has the depth to match therewith;
The bottom plate (7) and lower shell (6) are integrally formed, or the close connection that cooperates, and are coated in junction
Sealant;
For the gas outlet (8) perpendicular to lower shell (6) side wall, center axis thereof is not more than 10cm with a distance from bottom plate (7);
The air exhauster (11) has display panel, whether for showing current open and the flow of gas bleeding;
The upper shell (3), upper press ring (2), lower pressure ring (5), lower shell (6), bottom plate (7), gas outlet (8) material be it is transparent
Or translucent rigid polymeric material;The escape pipe (9), buffering ball (12), lower liquid pipe (13), the material of exhaust tube (10) are
It is transparent or semitransparent;
The middle part of the lower liquid pipe (13) is equipped with counnter attack flow, which can only open downwards.
2. the preparation facilities of the composite material of graphene according to claim 1 and nanofiber and nano particle, special
Sign is:
The upper press ring rubber (1), lower pressure ring rubber (4) material be the heat cure butyl rubber of scratch-resistant, and surface has
Rough netted lines;
The upper shell (3), upper press ring (2), lower pressure ring (5), lower shell (6), bottom plate (7), gas outlet (8), counnter attack flow
Material is polypropylene or makrolon material;The escape pipe (9), buffering ball (12), lower liquid pipe (13), exhaust tube (10)
Material is epoxy resin;
The air exhauster has several gears, is evacuated air quantity between 0.5-5L/min, is supplied by the 12V DC electricity that alternating current is converted
Electricity.
3. the preparation method of the composite material of a kind of graphene and nanofiber and nano particle, using such as claim 2 institute
A kind of graphene stated is with the preparation facilities of nanofiber and the composite material of nano particle to implement, which is characterized in that including
Following steps:
1) electrospinning film preparation step: choosing appropriate PCL fiber and be added among the pure chloroform of 100ml analysis, ultrasonic disperse 15-30min,
Mass percent is obtained in the PCL fiber chloroform dispersion liquid of 3-7%;
Electrospinning voltages 10-15kV, extruded velocity 2-4ml/h are chosen, distance 20-30cm is received, 2h, environment temperature between when electrospinning
It is 4-8 DEG C, obtains PCL electrospinning film;
2) film gripping step: the PCL electrospinning film greater than upper press ring (2) or lower pressure ring (5) area chosen, successively using foot
Tetrahydrofuran, dehydrated alcohol, distilled water, the dehydrated alcohol of amount are respectively washed silicon wafer at least 1 time, after drying completely, after cleaning
PCL electrospinning film tense and be clamped between upper press ring rubber (1) and lower pressure ring rubber (4), make its corrugationless;
3) it graphene microchip dispersion solution preparing step: using prefabricated a large amount of expanded graphite lamellas as raw material, is passed through in dehydrated alcohol
The ultrasound removing of 1h or more generates graphene microchip;
The solvent absolute ethyl alcohol of graphene microchip is supplemented to 200ml or more, high strength supersonic shakes 3-5min, discards at once
The dispersion liquid of layer half, repeats above procedure at least 5-10 times, until the average radial size of graphene microchip is higher than 5-10um;
4) negative pressure attachment steps: by the graphene microchip mass percent containing aforementioned average radial size higher than 5-10um in 5-
Chloroform dispersion liquid 100-150ml between 10% is imported in upper shell (3) with pole jogging speed, is being inclined through 1-2min ultrasonic disperse
Be finished down finish after, by the air exhauster by 0.5-1.5L/min flow rate aspirate 2-5s after stop 5-8s in a manner of iterative cycles, directly
Observe that PCL electrospinning film drips without obvious liquid to through lower shell;The liquid of lower liquid pipe (13) outflow is received simultaneously with waste liquid cylinder
Recycling;
Step (4) preceding sections are repeated to operate 10-20 times;
Electrospinning film after attachment graphene microchip is cut into the circular portion adhered to by graphene, successively uses enough tetrahydro furans
Mutter, dehydrated alcohol, distilled water, dehydrated alcohol are respectively washed silicon wafer at least 1 time, are dried completely, it is multiple to obtain graphene PCL electrospinning film
Condensation material;
5) micro- carburising step: graphene PCL electrospinning film composite material being put and is evened up in the heating container, micro- at 210-225 DEG C
Be carbonized 30-90min;
6) hydro-thermal reaction step: 6) cobalt nitrate, zinc nitrate, thiocarbamide and urea according to the quality proportioning of 2:1:2:4 are dissolved in enough
In the mixed liquor of the dehydrated alcohol deionized water of 1:9 volume ratio, the lower reaction of strong stirring;4 DEG C at least three are heated-are cooled to repeatedly
It is secondary, the biuret of precipitation is removed, salting liquid is obtained;
The salting liquid of 100-150ml and 1-3g graphene PCL electrospinning film composite material are put into water heating kettle, at 200-220 DEG C
16-24h is reacted, is successively respectively washed silicon wafer 3-5 times using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol,
Cobalt sulfide zinc/graphene microchip/PCL electrospinning film composite material is obtained.
4. the preparation method of the composite material of a kind of graphene as claimed in claim 3 and nanofiber and nano particle,
It is characterized in that:
In step 1, ultrasonic disperse 20min obtains PCL fiber chloroform dispersion liquid of the mass percent 5%;Choose electrospinning voltages
10kV, extruded velocity 2.5ml/h, receive distance 20cm, electrospinning time 2h, and environment temperature is 4 DEG C;
In step 2, successively it is respectively washed silicon wafer 3 times using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol;
In step 3, high strength supersonic shakes 3min, discards the dispersion liquid of upper layer half at once, repeats above procedure at least 5 times,
Until the average radial size of graphene microchip is higher than 5um;
In step 4,6% chloroform dispersion liquid 120ml is imported in upper shell (3) with pole jogging speed, is being inclined through 1min ultrasonic disperse
Be finished down finish after, by the air exhauster by 0.6L/min flow rate aspirate 3s after stop 6s in a manner of iterative cycles;
In step 5, micro- carbonization 50min at 210 DEG C;
In step 6, the salting liquid of 120ml and 1.5g graphene PCL electrospinning film composite material are put into water heating kettle, at 205 DEG C
18h is reacted, is successively respectively washed silicon wafer 3 times using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol.
5. the preparation method of the composite material of a kind of graphene as claimed in claim 3 and nanofiber and nano particle,
It is characterized in that:
In step 1, ultrasonic disperse 25min obtains PCL fiber chloroform dispersion liquid of the mass percent 6%;Choose electrospinning voltages
12kV, extruded velocity 3.5ml/h, receive distance 25cm, electrospinning time 2h, and environment temperature is 5 DEG C;
In step 2, successively it is respectively washed silicon wafer 4 times using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol;
In step 3, high strength supersonic shakes 4min, discards the dispersion liquid of upper layer half at once, repeats above procedure at least 8 times,
Until the average radial size of graphene microchip is higher than 8um;
In step 4,6% chloroform dispersion liquid 140ml is imported in upper shell (3) with pole jogging speed, is being inclined through 2min ultrasonic disperse
Be finished down finish after, by the air exhauster by 1.2L/min flow rate aspirate 5s after stop 8s in a manner of iterative cycles;
In step 5, micro- carbonization 50min at 210 DEG C;
In step 6, the salting liquid of 140ml and 2.5g graphene PCL electrospinning film composite material are put into water heating kettle, at 215 DEG C
22h is reacted, is successively respectively washed silicon wafer 5 times using enough tetrahydrofurans, dehydrated alcohol, distilled water, dehydrated alcohol.
6. a kind of cobalt sulfide zinc/graphene microchip/PCL electrospinning film composite material uses a kind of graphene as claimed in claim 3
It is prepared with the preparation method of nanofiber and the composite material of nano particle, it is characterised in that:
Based on PCL electrospinning film of the one kind after partially carbonized, average radial size is dispersed between PCL fiber higher than 5-
The graphene microchip of 10um, is also dispersed with cobalt sulfide zinc nanoparticles between PCL fiber, and the graphene microchip accounts for composite wood
Expect that mass percent is greater than 3%, the cobalt sulfide zinc nanoparticles account for composite material mass percent greater than 5%.
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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 |
Cited By (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 |
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