CN103360616A - Method for preparing hybrid film through graphene/nano crystalline cellulose dispersion liquid - Google Patents
Method for preparing hybrid film through graphene/nano crystalline cellulose dispersion liquid Download PDFInfo
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Abstract
The invention relates to a method for preparing hybrid film through graphene/nano crystalline cellulose dispersion liquid. The preparation method comprises the following steps: respectively dispersing oxidized graphene obtained by oxidation treatment and nano crystalline cellulose in a dispersing agent, and then, gradually dripping nano crystalline cellulose dispersion liquid into oxidized graphene dispersion liquid to obtain graphene/nano crystalline cellulose dispersion liquid, adding a reducing agent under ultrasonic or mechanical stirring condition to reduce the oxidized graphene, inserting the crystalline cellulose between graphene pieces to prevent aggregation between the graphene layers and to form uniformly dispersed and stable graphene/nano crystalline cellulose dispersion liquid, and then, preparing a graphene/nano crystalline cellulose hybrid film through such methods as spin coating, spray coating, film casting, and the like. The prepared hybrid film has high uniformity, and the higher the content of the graphene in the hybrid film, the stronger the thermal stability and conductivity of the hybrid film are; the higher the content of nano crystalline cellulose in the hybrid film is, the smaller the contact angle of the hybrid film is, and the stronger the hydrophilicity is.
Description
Technical field
The present invention relates to a kind of preparation method of hybridized film, be specifically related to the preparation method of Graphene/receive crystal fiber element hybridized film, belong to technical field of material.
Background technology
Graphene is a kind of carbonaceous material by the tightly packed bi-dimensional cellular shape carbon atom crystal that forms of monolayer carbon atom.Since 2004 are found, just enjoyed physics and Material Field investigator's concern always.Its basic structural unit is stable six-ring, and this special structure makes it have the performance of many excellences.Such as its theoretical specific surface area up to 2600m
2/ g, thermal conductivity reaches 5000Wm
-1K
-1, high electronic mobility (15000cm/(V.s) under the room temperature), and the series of physical character such as special quantum hall effect and quantum tunneling effect.Because the property of Graphene has determined that it has a wide range of applications at aspects such as electromagnetism, sensor, medicine and pharmacology.
The preparation method of Graphene mainly contains micromechanics stripping method, oxidation reduction process, chemical Vapor deposition process etc., and wherein oxidation reduction process is easy to mass-producing realization and with low cost, is a kind of method that is most widely used at present.But in the process of reduction, the polarity oxy radical of graphene oxide surface band is such as hydroxyl, carboxyl etc., major part is removed gradually, and the Graphene that obtains is because surface oxygen functional group reduces, and surface potential reduces, cause Graphene bad dispersibility in solvent, and irreversible reunion occurs.Although can make graphene functionalized or add the reunion that the dispersion stabilizers such as tensio-active agent, biomacromolecule suppress graphene film by chemical modification, this method have not only increased cost, has also brought pollution problem.Mierocrystalline cellulose is synthetic by photosynthesis by plant, have inexpensive, degradable, environmentally friendly, do not produce the characteristics such as pollution.The cellulose crystals of nano-scale has the characteristic of many uniquenesses, such as huge specific surface area, superpower adsorptive power and high reactive behavior etc.Receiving crystal fiber element surface is rich in the polarity oxy radical, can and the remaining oxy radical in Graphene surface between the noncovalent interactions such as hydrogen bond and electrostatic force occur.
Domestic and international research for the Graphene hybridized film, in existing technology, China Patent Publication No. CN102659096A, open day 2012.09.12, denomination of invention is " a kind of graphene dispersing solution and thin film technology method thereof ", this application scheme adopts organic solvent at high temperature to process graphite, then peel off dispersion with the graphite of pyroprocessing is ultrasonic in solvent, obtain stable graphene dispersing solution after centrifugal, but temperature of reaction is high, condition is harsh.China Patent Publication No. CN102583335A, open day 2012.07.18, denomination of invention is " a kind of preparation method of graphene uniform dispersion ", this application scheme adopts mixes Graphite Powder 99 with water phase surfactant mixture, put into to be incubated to process under the rear High Temperature High Pressure of autoclave and obtain slurry, slurry is carried out obtaining after high speed centrifugation separates the dispersion liquid of Graphene, but, the tensio-active agent that the method is used in the process of preparation graphene dispersing solution is big for environment pollution, is difficult to whole unstripped graphite granules and the many Graphenes of the number of plies are precipitated by centrifugation.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to overcome the problem that shows bad dispersibility in common solvent when Graphene disperses, make graphene oxide in dispersion agent, peel off the formation laminated structure by ultrasonication, then the crystal fiber element dispersion liquid of will receiving adds in the graphene oxide dispersion liquid, adding reductive agent forms under ultrasonication and is uniformly dispersed again, stable Graphene/plain the dispersion liquid of the crystal fiber of receiving, then prepare Graphene/plain hybridized film of the crystal fiber of receiving by methods such as spin coating or spraying or casting film-formings, to achieve these goals, technical solution of the present invention is:
A kind of Graphene/crystal fiber element the dispersion liquid of receiving prepares the method for hybridized film, and described preparation method carries out according to the following steps:
The graphene oxide that a will obtain after oxide treatment and the crystal fiber element of receiving add respectively in the dispersion agent, respectively compound concentration be the graphene oxide dispersion liquid of 0.1～1mg/ml and concentration be 5～20mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 1～2h, the power of ultrasonic device is 80～150W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 30～60ml/min, dripping quantity is 20～60:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 0.5～1h and regulate pH to 5～7, obtain the graphene oxide that concentration is 1.5～15.5mg/ml/plain dispersion liquid of the crystal fiber of receiving.
Wherein, described graphene oxide diameter is 0.5～3 μ m, and the crystal fiber element length of receiving is 0.5～1 μ m, and diameter is 30～100nm.
Described dispersion agent is one or more the mixing in deionized water or ethanol or ethylene glycol or the propyl alcohol;
The graphene oxide that b will obtain through a step/crystal fiber element dispersion liquid of receiving places 90～95 ℃ water bath with thermostatic control, mass ratio according to graphene oxide and reductive agent is that 10:6～10 dropwise add reductive agent, under ultrasonic or mechanical stirring condition, react 4～6h, the power of ultrasonic device is 80～150w, mechanical stirring speed is 500～1000r/min, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
Wherein, described reductive agent is hydrazine hydrate or quadrol or a kind of in the n-Butyl Amine 99.
The Graphene that c will obtain through the b step/crystal fiber element dispersion liquid of receiving adopts spin-coating method or spraying method or casting filming therapy to prepare Graphene/receive crystal fiber element hybridized film.
Owing to having adopted above technical scheme, a kind of Graphene of the present invention/thermotropic liquid crystal full-aromatic polyester composite manufacture method has the following advantages:
The preparation method of 1 Graphene of the present invention/receive crystal fiber element hybridized film, employing is dispersed in respectively graphene oxide and the crystal fiber element of receiving in the dispersion agent, prepare certain density dispersion liquid, carry out respectively ultra-sonic dispersion, ultrasonication makes graphene oxide peel off the formation laminated structure, then the crystal fiber element dispersion liquid of will receiving adds in the graphene oxide dispersion liquid, continue ultra-sonic dispersion, the noncovalent interactions such as the hydrogen bond of oxy radical that crystal fiber element surface is rich in and the formation of graphene oxide lamella and electrostatic force are received in utilization, obtain graphene oxide/plain dispersion liquid of the crystal fiber of receiving, add again reductive agent, graphene oxide reduces under ultrasound condition, the most of oxy radical in surface is removed, because the crystal fiber element of receiving interts between graphene sheet layer, so that Graphene can not reunited between layers, formation is uniformly dispersed, then the stable Graphene/plain dispersion liquid of the crystal fiber of receiving adopts spin coating with the Graphene/crystal fiber element dispersion liquid of receiving, spraying, the methods such as casting film-forming are prepared Graphene/plain hybridized film of the crystal fiber of receiving.Preparation method's technique of the present invention is simple, and the preparation process environmentally safe can be realized scale operation.
2 preparation methods of the present invention preparation the Graphene/crystal fiber element hybridized film of receiving have high uniformity, Graphene/crystal fiber element the hybridized film of receiving at high temperature keeps dimensional stability, Graphene content is higher in the hybridized film, and thermostability and the conductivity of hybridized film are stronger; The content of crystal fiber element received in the hybridized film is higher, and the contact angle of hybridized film is less, and hydrophilicity is stronger.
Embodiment
Below in conjunction with specific embodiment the present invention is done and to describe in further detail.
The preparation method of a kind of Graphene/receive crystal fiber element hybridized film, described preparation method may further comprise the steps:
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C adds respectively above-mentioned graphene oxide and the crystal fiber element of receiving in the dispersion agent, respectively compound concentration be the graphene oxide dispersion liquid of 0.1～1mg/ml and concentration be 5～20mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 1～2h, the power of ultrasonic device is 80～150W, graphene oxide is peeled off into laminated structure in the ultrasonic procedure, the crystal fiber element rhabdolith of receiving of reuniting in the plain dispersion liquid of the crystal fiber of receiving scatter, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 30～60ml/min, dripping quantity is 20～60:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 0.5～1h and regulate pH to 5～7, the noncovalent interactions such as the hydrogen bond that the oxy radical that be rich on the plain surface of the crystal fiber of receiving in the ultrasonic procedure and graphene oxide lamella form and electrostatic force, the crystal fiber element rhabdolith of receiving interts in graphene oxide lamella structure, obtains the graphene oxide that concentration is 1.5～15.5mg/ml/plain dispersion liquid of the crystal fiber of receiving.
Wherein, described graphene oxide diameter is 0.5～3 μ m, and the crystal fiber element length of receiving is 0.5～1 μ m, and diameter is 30～100nm.
Described dispersion agent is one or more the mixing in deionized water or ethanol or ethylene glycol or the propyl alcohol.
The graphene oxide that d will obtain through the c step/crystal fiber element dispersion liquid of receiving places 90～95 ℃ water bath with thermostatic control, mass ratio according to graphene oxide and reductive agent is that 10:6～10 dropwise add reductive agent, under ultrasonic or mechanical stirring condition, react 4～6h, the power of ultrasonic device is 80～150w, mechanical stirring speed is 500～1000r/min, graphene oxide reduces in reaction process, the most of oxy radical in surface is removed, because the crystal fiber element of receiving interts between graphene sheet layer, so that Graphene can not reunited between layers, be uniformly dispersed, stable Graphene/plain the dispersion liquid of the crystal fiber of receiving.
Wherein, described reductive agent is hydrazine hydrate or quadrol or a kind of in the n-Butyl Amine 99.
E will adopt spin-coating method in the existing technique or spraying method or casting filming therapy to prepare Graphene/receive crystal fiber element hybridized film through Graphene that the d step obtains/crystal fiber element dispersion liquid of receiving.
Specific embodiment
Embodiment 1
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C adds above-mentioned graphene oxide and the crystal fiber element of receiving respectively in deionized water or ethanol or ethylene glycol or the propyl alcohol, respectively compound concentration be the graphene oxide dispersion liquid of 0.1mg/ml and concentration be 5mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 1h, the power of ultrasonic device is 80W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 30/min, dripping quantity is 20:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 0.5h and regulate pH to 5, obtain the graphene oxide that concentration is 1.5mg/ml/plain dispersion liquid of the crystal fiber of receiving.
D places 90 ℃ water bath with thermostatic control with the graphene oxide/crystal fiber element dispersion liquid of receiving, mass ratio according to graphene oxide and hydrazine hydrate is that 10:6 dropwise adds hydrazine hydrate, under ultrasound condition, react 4h, the power of ultrasonic device is 80w, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
E will prepare Graphene/plain hybridized film of the crystal fiber of receiving through the spin-coating method that Graphene/the crystal fiber element dispersion liquid employing of receiving has now in the technique that the d step obtains.After tested, the Graphene of the preparation/crystal fiber element hybridized film of receiving at high temperature keeps dimensional stability, and thermostability and electroconductibility are good.
Embodiment 2
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C adds respectively above-mentioned graphene oxide and the crystal fiber element of receiving in the ethanol, respectively compound concentration be the graphene oxide dispersion liquid of 0.2mg/ml and concentration be 6mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 1.5h, the power of ultrasonic device is 90W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 40ml/min, dripping quantity is 30:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 0.6h and regulate pH to 6, obtain the graphene oxide that concentration is 3.1mg/ml/plain dispersion liquid of the crystal fiber of receiving.
D places 95 ℃ water bath with thermostatic control with the graphene oxide/crystal fiber element dispersion liquid of receiving, mass ratio according to graphene oxide and quadrol is that 10:7 dropwise adds quadrol, under ultrasound condition, react 5h, the power of ultrasonic device is 90w, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
E will prepare Graphene/plain hybridized film of the crystal fiber of receiving through the spraying method that Graphene/the crystal fiber element dispersion liquid employing of receiving has now in the technique that the d step obtains.After tested, the Graphene of the preparation/crystal fiber element hybridized film of receiving at high temperature keeps dimensional stability, and thermostability and electroconductibility are good.
Embodiment 3
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C adds respectively above-mentioned graphene oxide and the crystal fiber element of receiving in the ethylene glycol, respectively compound concentration be the graphene oxide dispersion liquid of 0.5mg/ml and concentration be 8mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 2h, the power of ultrasonic device is 100W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 50ml/min, dripping quantity is 40:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 0.8h and regulate pH to 7, obtain the graphene oxide that concentration is 5.8mg/ml/plain dispersion liquid of the crystal fiber of receiving.
D places 95 ℃ water bath with thermostatic control with the graphene oxide/crystal fiber element dispersion liquid of receiving, mass ratio according to graphene oxide and n-Butyl Amine 99 is that 10:8 dropwise adds n-Butyl Amine 99, under ultrasound condition, react 6h, the power of ultrasonic device is 100w, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
E will prepare Graphene/plain hybridized film of the crystal fiber of receiving through the casting filming therapy that Graphene/the crystal fiber element dispersion liquid employing of receiving has now in the technique that the d step obtains.After tested, the Graphene of the preparation/crystal fiber element hybridized film of receiving at high temperature keeps dimensional stability, and thermostability and electroconductibility are good.
Embodiment 4
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C adds respectively above-mentioned graphene oxide and the crystal fiber element of receiving in the propyl alcohol, respectively compound concentration be the graphene oxide dispersion liquid of 1mg/ml and concentration be 10mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 2h, the power of ultrasonic device is 110W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 60ml/min, dripping quantity is 50:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 0.9h and regulate pH to 7, obtain the graphene oxide that concentration is 8.5mg/ml/plain dispersion liquid of the crystal fiber of receiving.
D places 95 ℃ water bath with thermostatic control with the graphene oxide/crystal fiber element dispersion liquid of receiving, mass ratio according to graphene oxide and hydrazine hydrate is that 10:9 dropwise adds hydrazine hydrate, under ultrasound condition, react 6h, the power of ultrasonic device is 110w, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
E will prepare Graphene/plain hybridized film of the crystal fiber of receiving through the spin-coating method that Graphene/the crystal fiber element dispersion liquid employing of receiving has now in the technique that the d step obtains.After tested, the Graphene of the preparation/crystal fiber element hybridized film of receiving at high temperature keeps dimensional stability, and thermostability and electroconductibility are good.
Embodiment 5
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C prepares dispersion agent with deionized water and ethanol according to volume ratio 1:1, above-mentioned graphene oxide and the crystal fiber element of receiving are added respectively in this dispersion agent, respectively compound concentration be the graphene oxide dispersion liquid of 1mg/ml and concentration be 15mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 2h, the power of ultrasonic device is 130W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 1h and regulate pH to 7, obtain the graphene oxide that concentration is 12.2mg/ml/plain dispersion liquid of the crystal fiber of receiving.
D places 95 ℃ water bath with thermostatic control with the graphene oxide/crystal fiber element dispersion liquid of receiving, mass ratio according to graphene oxide and hydrazine hydrate is that 10:10 dropwise adds hydrazine hydrate, under ultrasound condition, react 6h, the power of ultrasonic device is 130w, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
E will prepare Graphene/plain hybridized film of the crystal fiber of receiving through the spin-coating method that Graphene/the crystal fiber element dispersion liquid employing of receiving has now in the technique that the d step obtains.After tested, the Graphene of the preparation/crystal fiber element hybridized film of receiving at high temperature keeps dimensional stability, and thermostability and electroconductibility are good.
Embodiment 6
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C prepares dispersion agent with ethanol and propyl alcohol according to volume ratio 1:1, add respectively above-mentioned graphene oxide and the crystal fiber element of receiving in the dispersion agent, compound concentration be the graphene oxide dispersion liquid of 1mg/ml and concentration be 20mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 2h, the power of ultrasonic device is 150W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 1h and regulate pH to 7, obtain the graphene oxide that concentration is 15.5mg/ml/plain dispersion liquid of the crystal fiber of receiving.
D places 95 ℃ water bath with thermostatic control with the graphene oxide/crystal fiber element dispersion liquid of receiving, mass ratio according to graphene oxide and hydrazine hydrate is that 10:10 dropwise adds hydrazine hydrate, under ultrasound condition, react 6h, the power of ultrasonic device is 50w, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
E will prepare Graphene/plain hybridized film of the crystal fiber of receiving through the spin-coating method that Graphene/the crystal fiber element dispersion liquid employing of receiving has now in the technique that the d step obtains.After tested, the Graphene of the preparation/crystal fiber element hybridized film of receiving at high temperature keeps dimensional stability, and thermostability and electroconductibility are good.
Embodiment 7
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C prepares dispersion agent with ethanol and propyl alcohol according to volume ratio 1:1, add respectively above-mentioned graphene oxide and the crystal fiber element of receiving in the dispersion agent, compound concentration be the graphene oxide dispersion liquid of 1mg/ml and concentration be 20mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 2h, the power of ultrasonic device is 150W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 1h and regulate pH to 7, obtain the graphene oxide that concentration is 15.5mg/ml/plain dispersion liquid of the crystal fiber of receiving.
D places 95 ℃ water bath with thermostatic control with the graphene oxide/crystal fiber element dispersion liquid of receiving, mass ratio according to graphene oxide and hydrazine hydrate is that 10:10 dropwise adds hydrazine hydrate, under the mechanical stirring condition, react 6h, stir speed (S.S.) is 500r/min, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
E will prepare Graphene/plain hybridized film of the crystal fiber of receiving through the spin-coating method that Graphene/the crystal fiber element dispersion liquid employing of receiving has now in the technique that the d step obtains.After tested, the Graphene of the preparation/crystal fiber element hybridized film of receiving at high temperature keeps dimensional stability, and thermostability and electroconductibility are good.
Embodiment 8
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C prepares dispersion agent with ethanol and propyl alcohol according to volume ratio 1:1, add respectively above-mentioned graphene oxide and the crystal fiber element of receiving in the dispersion agent, compound concentration be the graphene oxide dispersion liquid of 1mg/ml and concentration be 20mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 2h, the power of ultrasonic device is 150W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 1h and regulate pH to 7, obtain the graphene oxide that concentration is 15.5mg/ml/plain dispersion liquid of the crystal fiber of receiving.
D places 95 ℃ water bath with thermostatic control with the graphene oxide/crystal fiber element dispersion liquid of receiving, mass ratio according to graphene oxide and hydrazine hydrate is that 10:10 dropwise adds hydrazine hydrate, under the mechanical stirring condition, react 6h, stir speed (S.S.) is 800r/min, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
E will prepare Graphene/plain hybridized film of the crystal fiber of receiving through the spin-coating method that Graphene/the crystal fiber element dispersion liquid employing of receiving has now in the technique that the d step obtains.After tested, the Graphene of the preparation/crystal fiber element hybridized film of receiving at high temperature keeps dimensional stability, and thermostability and electroconductibility are good.
Embodiment 9
The preoxidation of a graphite: the vitriol oil of getting 30ml joins in the there-necked flask of 500ml, then taking by weighing the 5g Potassium Persulphate slowly joins in the vitriol oil, the Vanadium Pentoxide in FLAKES that adds again 5g, be warming up to 80 ℃, then the Graphite Powder 99 that adds 3g, reaction 6h, reaction finishes filtration washing extremely through check sulfate radical-free ion, and then dry by the fire 3h in 60 ℃ the vacuum drying oven, obtain the preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil that measures 200ml joins in the there-necked flask of 500ml, place 0 ℃ ice bath, the Graphene that slowly adds preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 ℃ and keep 3h, then be warming up to 95 ℃ of restir 15min, then adding reaction solution transfers in the beaker of 1000ml, the deionized water that adds again 600ml, add again the 6ml30% hydrogen peroxide, then filter, use successively 10% hydrochloric acid, deionized water wash is to neutral, then in 60 ℃ vacuum drying oven, dry by the fire 3h, obtain graphene oxide.
B receives the preparation of crystal fiber element: preparation 100ml massfraction is 64% sulfuric acid, join in the there-necked flask of 200ml, then taking by weighing the absorbent cotton that 5g shreds joins in the sulfuric acid, be warming up to 45 ℃, stirring reaction 50min, when finishing, reaction can see the milky crystal fiber element suspension of receiving, move in the beaker of 1500ml receiving crystal fiber element suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min until supernatant liquor pH greater than 1, after the centrifugal washing receive crystal fiber element suspension put into dialysis tubing dialysis a couple of days to a bag inner suspension liquid pH be about 7, then at-50 ℃ of lower vacuum lyophilization 24h, what obtain white receives crystal fiber element powder.
C prepares dispersion agent with ethanol and propyl alcohol according to volume ratio 1:1, add respectively above-mentioned graphene oxide and the crystal fiber element of receiving in the dispersion agent, compound concentration be the graphene oxide dispersion liquid of 1mg/ml and concentration be 20mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 2h, the power of ultrasonic device is 150W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 1h and regulate pH to 7, obtain the graphene oxide that concentration is 15.5mg/ml/plain dispersion liquid of the crystal fiber of receiving.
D places 95 ℃ water bath with thermostatic control with the graphene oxide/crystal fiber element dispersion liquid of receiving, mass ratio according to graphene oxide and hydrazine hydrate is that 10:10 dropwise adds hydrazine hydrate, under the mechanical stirring condition, react 6h, stir speed (S.S.) is 1000r/min, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives.
E will prepare Graphene/plain hybridized film of the crystal fiber of receiving through the spin-coating method that Graphene/the crystal fiber element dispersion liquid employing of receiving has now in the technique that the d step obtains.After tested, the Graphene of the preparation/crystal fiber element hybridized film of receiving at high temperature keeps dimensional stability, and thermostability and electroconductibility are good.
Claims (1)
1. Graphene/crystal fiber element the dispersion liquid of receiving prepares the method for hybridized film, and it is characterized in that: described preparation method carries out according to the following steps:
The graphene oxide that a will obtain after oxide treatment and the crystal fiber element of receiving add respectively in the dispersion agent, respectively compound concentration be the graphene oxide dispersion liquid of 0.1 ~ 1mg/ml and concentration be 5 ~ 20mg/ml receive crystal fiber element dispersion liquid, ultra-sonic dispersion 1 ~ 2h, the power of ultrasonic device is 80 ~ 150W, then the crystal fiber element dispersion liquid of will receiving dropwise adds in the graphene oxide dispersion liquid, rate of addition is 30 ~ 60ml/min, dripping quantity is 20 ~ 60:1 according to receiving crystal fiber element with the graphene oxide mass ratio, continue ultra-sonic dispersion 0.5 ~ 1h and regulate pH to 5 ~ 7, obtain the graphene oxide that concentration is 1.5 ~ 15.5mg/ml/plain dispersion liquid of the crystal fiber of receiving;
Wherein, described graphene oxide diameter is 0.5 ~ 3 μ m, and the crystal fiber element length of receiving is 0.5 ~ 1 μ m, and diameter is 30 ~ 100nm;
Described dispersion agent is one or more the mixing in deionized water or ethanol or ethylene glycol or the propyl alcohol;
The graphene oxide that b will obtain through a step/crystal fiber element dispersion liquid of receiving places 90 ~ 95 ℃ water bath with thermostatic control, mass ratio according to graphene oxide and reductive agent is that 10:6 ~ 10 dropwise add reductive agent, under ultrasonic or mechanical stirring condition, react 4 ~ 6h, the power of ultrasonic device is 80 ~ 150w, mechanical stirring speed is 500 ~ 1000r/min, and crystal fiber element dispersion liquid is uniformly dispersed, stable Graphene/receives;
Wherein, described reductive agent is hydrazine hydrate or quadrol or a kind of in the n-Butyl Amine 99;
The Graphene that c will obtain through the b step/crystal fiber element dispersion liquid of receiving adopts spin-coating method or spraying method or casting filming therapy to prepare Graphene/receive crystal fiber element hybridized film.
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