CN103360616B - A kind of film through graphene/nano crystalline cellulose dispersion liquid prepares the method for hybridized film - Google Patents
A kind of film through graphene/nano crystalline cellulose dispersion liquid prepares the method for hybridized film Download PDFInfo
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Abstract
The present invention relates to a kind of method that film through graphene/nano crystalline cellulose dispersion liquid prepares hybridized film.Described preparation method adopts and the graphene oxide obtained after oxide treatment and crystalline cellulose of receiving is dispersed in respectively in dispersion agent, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, obtain graphene oxide/receive crystalline cellulose dispersion liquid, reductive agent redox graphene is added under ultrasonic or mechanical agitation, crystalline cellulose of receiving is interted at graphene film interlayer, Graphene can not be reunited between layers, formation is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid, then spin coating is adopted, spraying, the methods such as casting film-forming prepare graphene/nano crystalline cellulose hybridized film.The hybridized film of preparation has high uniformity, and in hybridized film, Graphene content is higher, and thermostability and the conductivity of hybridized film are stronger; The content of crystalline cellulose received in hybridized film is higher, and the contact angle of hybridized film is less, and hydrophilicity is stronger.
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/nano crystalline cellulose hybridized film, belong to technical field of material.
Background technology
Graphene is a kind of carbonaceous material of the bi-dimensional cellular shape carbon atom crystal tightly packed by monolayer carbon atom.Since being found from 2004, just enjoyed the concern of physics and Material Field investigator 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 is up to 2600m
2/ g, thermal conductivity reaches 5000Wm
-1k
-1, electronic mobility (15000cm/(V.s) high under room temperature), and the series of physical character such as special quantum hall effect and quantum tunneling effect.Due to the property of Graphene, determine it and have a wide range of applications in electromagnetism, sensor, medicine and pharmacology etc.
The preparation method of Graphene mainly contains micromechanics stripping method, oxidation reduction process, chemical Vapor deposition process etc., wherein oxidation reduction process be easy to mass-producing realize and with low cost, be a kind of method be most widely used at present.But in the process of reduction, the polarity oxy radical of surface of graphene oxide band, as hydroxyl, carboxyl etc., major part is removed gradually, and the Graphene obtained reduces due to surface oxygen functional group, and surface potential reduces, cause Graphene bad dispersibility in a solvent, and irreversible reunion occurs.Although graphene functionalized or dispersion stabilizer such as interpolation tensio-active agent, biomacromolecule etc. can be made to suppress the reunion of graphene film by chemical modification, this method not only increases cost, also brings pollution problem.Mierocrystalline cellulose is synthesized by photosynthesis by plant, have inexpensive, degradable, environmentally friendly, do not produce the features such as pollution.The cellulose crystals of nano-scale has the characteristic of many uniquenesses, as huge specific surface area, superpower adsorptive power and high reactive behavior etc.Crystalline cellulose rich surface of receiving containing polarity oxy radical, can and the oxy radical of graphenic surface remnants between there is the noncovalent interaction such as hydrogen bond and electrostatic force.
Both at home and abroad for the research of Graphene hybridized film, in existing technology, China Patent Publication No. CN102659096A, publication date 2012.09.12, denomination of invention is " preparation method of a kind of graphene dispersing solution and film thereof ", and this application scheme adopts organic solvent at high temperature to process graphite, then by the ultrasonic stripping dispersion in a solvent of the graphite of pyroprocessing, obtain stable graphene dispersing solution after centrifugal, but temperature of reaction is high, condition is harsh.China Patent Publication No. CN102583335A, publication date 2012.07.18, denomination of invention is " a kind of preparation method of graphene uniform dispersion ", this application scheme adopts and is mixed with water phase surfactant mixture by Graphite Powder 99, after putting into autoclave, under High Temperature High Pressure, isothermal holding obtains slurry, the dispersion liquid of Graphene is obtained after high speed centrifugation separation is carried out to slurry, but, the tensio-active agent that the method uses in the process preparing graphene dispersing solution is big for environment pollution, be difficult to whole unstripped graphite granules and the many Graphene of the number of plies to precipitate by centrifugation.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to overcome the problem showing bad dispersibility when Graphene disperses in common solvent, make graphene oxide in dispersion agent, peel off formation sheet Rotating fields by ultrasonication, then crystalline cellulose dispersion liquid of receiving adds in graphene oxide dispersion, add reductive agent again to be formed under ultrasonication and be uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid, then graphene/nano crystalline cellulose hybridized film is prepared by spin coating or the method such as spraying or casting film-forming, to achieve these goals, technical solution of the present invention is:
Film through graphene/nano crystalline cellulose dispersion liquid prepares a method for hybridized film, and described preparation method carries out according to the following steps:
The graphene oxide obtained after oxide treatment and crystalline cellulose of receiving add in dispersion agent by a respectively, respectively compound concentration to be the graphene oxide dispersion of 0.1 ~ 1mg/ml and concentration be 5 ~ 20mg/ml receive crystalline cellulose dispersion liquid, ultrasonic disperse 1 ~ 2h, the power of ultrasonic device is 80 ~ 150W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 30 ~ 60ml/min, dripping quantity is 20 ~ 60:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 0.5 ~ 1h and regulate pH to 5 ~ 7, obtain graphene oxide that concentration is 1.5 ~ 15.5mg/ml/receive crystalline cellulose dispersion liquid.
Wherein, described graphene oxide diameter is 0.5 ~ 3 μm, and crystalline cellulose length of receiving is 0.5 ~ 1 μm, and diameter is 30 ~ 100nm.
Described dispersion agent is the mixing of one or more in deionized water or ethanol or ethylene glycol or propyl alcohol;
The graphene oxide obtained through a step/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 90 ~ 95 DEG C by b, be that 10:6 ~ 10 dropwise add reductive agent according to the mass ratio of graphene oxide and reductive agent, reaction 4 ~ 6h under ultrasonic or mechanical agitation, the power of ultrasonic device is 80 ~ 150w, mechanical stirring speed is 500 ~ 1000r/min, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
Wherein, described reductive agent is hydrazine hydrate or quadrol or to the one in n-Butyl Amine 99.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through b step adopts spin-coating method or spraying method or casting filming therapy to prepare graphene/nano crystalline cellulose hybridized film by c.
Owing to have employed above technical scheme, the preparation method of a kind of Graphene of the present invention/thermotropic liquid crystal full-aromatic polyester matrix material has the following advantages:
The preparation method of 1 graphene/nano crystalline cellulose hybridized film of the present invention, adopt and graphene oxide and crystalline cellulose of receiving are dispersed in dispersion agent respectively, prepare certain density dispersion liquid, carry out ultrasonic disperse respectively, ultrasonication makes graphene oxide peel off formation sheet Rotating fields, then crystalline cellulose dispersion liquid of receiving adds in graphene oxide dispersion, continue ultrasonic disperse, utilize and receive oxy radical that crystalline cellulose rich surface contains and the noncovalent interaction such as the hydrogen bond that graphene oxide lamella is formed and electrostatic force, obtain graphene oxide/receive crystalline cellulose dispersion liquid, add reductive agent again, under ultrasound condition, graphene oxide reduces, the most of oxy radical in surface is removed, intert between graphene sheet layer owing to receiving crystalline cellulose, Graphene can not be reunited between layers, formation is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid, then film through graphene/nano crystalline cellulose dispersion liquid is adopted spin coating, spraying, the methods such as casting film-forming prepare graphene/nano crystalline cellulose hybridized film.Preparation method's technique of the present invention is simple, and preparation process environmentally safe, can realize scale operation.
2 preparation methods of the present invention prepare graphene/nano crystalline cellulose hybridized film there is high uniformity, graphene/nano crystalline cellulose hybridized film at high temperature keeps dimensional stability, in hybridized film, Graphene content is higher, and thermostability and the conductivity of hybridized film are stronger; The content of crystalline cellulose received in 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 described in further detail.
A preparation method for graphene/nano crystalline cellulose hybridized film, described preparation method comprises the following steps:
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Above-mentioned graphene oxide and crystalline cellulose of receiving add in dispersion agent by c respectively, respectively compound concentration to be the graphene oxide dispersion of 0.1 ~ 1mg/ml and concentration be 5 ~ 20mg/ml receive crystalline cellulose dispersion liquid, ultrasonic disperse 1 ~ 2h, the power of ultrasonic device is 80 ~ 150W, in ultrasonic procedure, graphene oxide peels off into laminated structure, the crystalline cellulose rhabdolith of receiving of reuniting in crystalline cellulose dispersion liquid of receiving scatter, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 30 ~ 60ml/min, dripping quantity is 20 ~ 60:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 0.5 ~ 1h and regulate pH to 5 ~ 7, the oxy radical that crystalline cellulose rich surface of receiving in ultrasonic procedure contains and the noncovalent interaction such as the hydrogen bond that graphene oxide lamella is formed and electrostatic force, crystalline cellulose rhabdolith of receiving interts in graphene oxide laminated structure, obtain graphene oxide that concentration is 1.5 ~ 15.5mg/ml/receive crystalline cellulose dispersion liquid.
Wherein, described graphene oxide diameter is 0.5 ~ 3 μm, and crystalline cellulose length of receiving is 0.5 ~ 1 μm, and diameter is 30 ~ 100nm.
Described dispersion agent is the mixing of one or more in deionized water or ethanol or ethylene glycol or propyl alcohol.
The graphene oxide obtained through step c/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 90 ~ 95 DEG C by d, be that 10:6 ~ 10 dropwise add reductive agent according to the mass ratio of graphene oxide and reductive agent, reaction 4 ~ 6h under ultrasonic or mechanical agitation, the power of ultrasonic device is 80 ~ 150w, mechanical stirring speed is 500 ~ 1000r/min, in reaction process, graphene oxide reduces, the most of oxy radical in surface is removed, intert between graphene sheet layer owing to receiving crystalline cellulose, Graphene can not be reunited between layers, be uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
Wherein, described reductive agent is hydrazine hydrate or quadrol or to the one in n-Butyl Amine 99.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the spin-coating method in existing technique or spraying method or casting filming therapy to prepare graphene/nano crystalline cellulose hybridized film by e.
Specific embodiment
Embodiment 1
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Above-mentioned graphene oxide and crystalline cellulose of receiving add in deionized water or ethanol or ethylene glycol or propyl alcohol by c respectively, respectively compound concentration to be the graphene oxide dispersion of 0.1mg/ml and concentration be 5mg/ml receive crystalline cellulose dispersion liquid, ultrasonic disperse 1h, the power of ultrasonic device is 80W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 30/min, dripping quantity is 20:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 0.5h and regulate pH to 5, obtain graphene oxide that concentration is 1.5mg/ml/receive crystalline cellulose dispersion liquid.
Graphene oxide/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 90 DEG C by d, be that 10:6 dropwise adds hydrazine hydrate according to the mass ratio of graphene oxide and hydrazine hydrate, 4h is reacted under ultrasound condition, the power of ultrasonic device is 80w, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the spin-coating method in existing technique to prepare graphene/nano crystalline cellulose hybridized film by e.After tested, the graphene/nano crystalline cellulose hybridized film of preparation at high temperature keeps dimensional stability, thermostability and electroconductibility good.
Embodiment 2
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Above-mentioned graphene oxide and crystalline cellulose of receiving add in ethanol by c respectively, respectively compound concentration to be the graphene oxide dispersion of 0.2mg/ml and concentration be 6mg/ml receive crystalline cellulose dispersion liquid, ultrasonic disperse 1.5h, the power of ultrasonic device is 90W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 40ml/min, dripping quantity is 30:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 0.6h and regulate pH to 6, obtain graphene oxide that concentration is 3.1mg/ml/receive crystalline cellulose dispersion liquid.
Graphene oxide/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 95 DEG C by d, be that 10:7 dropwise adds quadrol according to the mass ratio of graphene oxide and quadrol, 5h is reacted under ultrasound condition, the power of ultrasonic device is 90w, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the spraying method in existing technique to prepare graphene/nano crystalline cellulose hybridized film by e.After tested, the graphene/nano crystalline cellulose hybridized film of preparation at high temperature keeps dimensional stability, thermostability and electroconductibility good.
Embodiment 3
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Above-mentioned graphene oxide and crystalline cellulose of receiving add in ethylene glycol by c respectively, respectively compound concentration to be the graphene oxide dispersion of 0.5mg/ml and concentration be 8mg/ml receive crystalline cellulose dispersion liquid, ultrasonic disperse 2h, the power of ultrasonic device is 100W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 50ml/min, dripping quantity is 40:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 0.8h and regulate pH to 7, obtain graphene oxide that concentration is 5.8mg/ml/receive crystalline cellulose dispersion liquid.
Graphene oxide/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 95 DEG C by d, be that 10:8 dropwise adds n-Butyl Amine 99 according to the mass ratio of graphene oxide and n-Butyl Amine 99,6h is reacted under ultrasound condition, the power of ultrasonic device is 100w, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the casting filming therapy in existing technique to prepare graphene/nano crystalline cellulose hybridized film by e.After tested, the graphene/nano crystalline cellulose hybridized film of preparation at high temperature keeps dimensional stability, thermostability and electroconductibility good.
Embodiment 4
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Above-mentioned graphene oxide and crystalline cellulose of receiving add in propyl alcohol by c respectively, respectively compound concentration to be the graphene oxide dispersion of 1mg/ml and concentration be 10mg/ml receive crystalline cellulose dispersion liquid, ultrasonic disperse 2h, the power of ultrasonic device is 110W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 60ml/min, dripping quantity is 50:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 0.9h and also regulate pH to 7, obtain graphene oxide that concentration is 8.5mg/ml/receive crystalline cellulose dispersion liquid.
Graphene oxide/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 95 DEG C by d, be that 10:9 dropwise adds hydrazine hydrate according to the mass ratio of graphene oxide and hydrazine hydrate, 6h is reacted under ultrasound condition, the power of ultrasonic device is 110w, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the spin-coating method in existing technique to prepare graphene/nano crystalline cellulose hybridized film by e.After tested, the graphene/nano crystalline cellulose hybridized film of preparation at high temperature keeps dimensional stability, thermostability and electroconductibility good.
Embodiment 5
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Deionized water and ethanol are prepared dispersion agent according to volume ratio 1:1 by c, above-mentioned graphene oxide and crystalline cellulose of receiving are added in this dispersion agent respectively, respectively compound concentration to be the graphene oxide dispersion of 1mg/ml and concentration be 15mg/ml receive crystalline cellulose dispersion liquid, ultrasonic disperse 2h, the power of ultrasonic device is 130W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 1h and regulate pH to 7, obtain graphene oxide that concentration is 12.2mg/ml/receive crystalline cellulose dispersion liquid.
Graphene oxide/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 95 DEG C by d, be that 10:10 dropwise adds hydrazine hydrate according to the mass ratio of graphene oxide and hydrazine hydrate, 6h is reacted under ultrasound condition, the power of ultrasonic device is 130w, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the spin-coating method in existing technique to prepare graphene/nano crystalline cellulose hybridized film by e.After tested, the graphene/nano crystalline cellulose hybridized film of preparation at high temperature keeps dimensional stability, thermostability and electroconductibility good.
Embodiment 6
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Ethanol and propyl alcohol are prepared dispersion agent according to volume ratio 1:1 by c, above-mentioned graphene oxide and crystalline cellulose of receiving are added in dispersion agent respectively, compound concentration to be the graphene oxide dispersion of 1mg/ml and concentration be 20mg/ml receives crystalline cellulose dispersion liquid, ultrasonic disperse 2h, the power of ultrasonic device is 150W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 1h and regulate pH to 7, obtain graphene oxide that concentration is 15.5mg/ml/receive crystalline cellulose dispersion liquid.
Graphene oxide/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 95 DEG C by d, be that 10:10 dropwise adds hydrazine hydrate according to the mass ratio of graphene oxide and hydrazine hydrate, 6h is reacted under ultrasound condition, the power of ultrasonic device is 50w, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the spin-coating method in existing technique to prepare graphene/nano crystalline cellulose hybridized film by e.After tested, the graphene/nano crystalline cellulose hybridized film of preparation at high temperature keeps dimensional stability, thermostability and electroconductibility good.
Embodiment 7
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Ethanol and propyl alcohol are prepared dispersion agent according to volume ratio 1:1 by c, above-mentioned graphene oxide and crystalline cellulose of receiving are added in dispersion agent respectively, compound concentration to be the graphene oxide dispersion of 1mg/ml and concentration be 20mg/ml receives crystalline cellulose dispersion liquid, ultrasonic disperse 2h, the power of ultrasonic device is 150W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 1h and regulate pH to 7, obtain graphene oxide that concentration is 15.5mg/ml/receive crystalline cellulose dispersion liquid.
Graphene oxide/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 95 DEG C by d, be that 10:10 dropwise adds hydrazine hydrate according to the mass ratio of graphene oxide and hydrazine hydrate, 6h is reacted under mechanical agitation, stir speed (S.S.) is 500r/min, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the spin-coating method in existing technique to prepare graphene/nano crystalline cellulose hybridized film by e.After tested, the graphene/nano crystalline cellulose hybridized film of preparation at high temperature keeps dimensional stability, thermostability and electroconductibility good.
Embodiment 8
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Ethanol and propyl alcohol are prepared dispersion agent according to volume ratio 1:1 by c, above-mentioned graphene oxide and crystalline cellulose of receiving are added in dispersion agent respectively, compound concentration to be the graphene oxide dispersion of 1mg/ml and concentration be 20mg/ml receives crystalline cellulose dispersion liquid, ultrasonic disperse 2h, the power of ultrasonic device is 150W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 1h and regulate pH to 7, obtain graphene oxide that concentration is 15.5mg/ml/receive crystalline cellulose dispersion liquid.
Graphene oxide/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 95 DEG C by d, be that 10:10 dropwise adds hydrazine hydrate according to the mass ratio of graphene oxide and hydrazine hydrate, 6h is reacted under mechanical agitation, stir speed (S.S.) is 800r/min, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the spin-coating method in existing technique to prepare graphene/nano crystalline cellulose hybridized film by e.After tested, the graphene/nano crystalline cellulose hybridized film of preparation at high temperature keeps dimensional stability, thermostability and electroconductibility good.
Embodiment 9
A graphite preoxidation: the vitriol oil getting 30ml joins in the there-necked flask of 500ml, then take 5g Potassium Persulphate slowly to join in the vitriol oil, add the Vanadium Pentoxide in FLAKES of 5g again, be warming up to 80 DEG C, then add the Graphite Powder 99 of 3g, reaction 6h, reaction terminates filtration washing extremely through inspection sulfate radical-free ion, and then dry 3h in the vacuum drying oven of 60 DEG C, obtain preoxidation Graphene.The secondary oxidation of preoxidation Graphene: the vitriol oil measuring 200ml joins in the there-necked flask of 500ml, be placed in the ice bath of 0 DEG C, slowly add the Graphene of preoxidation, and then slowly add the potassium permanganate of 30g, be warming up to 35 DEG C and maintain 3h, then be warming up to 95 DEG C and stir 15min again, then adding reaction solution transfers in the beaker of 1000ml, add the deionized water of 600ml again, add 6ml30% hydrogen peroxide again, then filter, use the hydrochloric acid of 10% successively, deionized water wash is to neutral, then in the vacuum drying oven of 60 DEG C, 3h is dried, obtain graphene oxide.
B receives the preparation of crystalline cellulose: preparation 100ml massfraction is the sulfuric acid of 64%, join in the there-necked flask of 200ml, then taking the absorbent cotton that 5g shreds joins in sulfuric acid, be warming up to 45 DEG C, stirring reaction 50min, milky crystalline cellulose suspension of receiving can be seen at the end of reaction, move in the beaker of 1500ml by receiving crystalline cellulose suspension, add 1000ml deionized water termination reaction, centrifugal washing under the rotating speed of 4500r/min is until supernatant liquor pH is greater than 1, the crystalline cellulose suspension of receiving after centrifugal washing, to put into dialysis tubing a couple of days of dialysing be about 7 to bag inner suspension liquid pH, then vacuum lyophilization 24h at-50 DEG C, what obtain white receives crystalline cellulose powder.
Ethanol and propyl alcohol are prepared dispersion agent according to volume ratio 1:1 by c, above-mentioned graphene oxide and crystalline cellulose of receiving are added in dispersion agent respectively, compound concentration to be the graphene oxide dispersion of 1mg/ml and concentration be 20mg/ml receives crystalline cellulose dispersion liquid, ultrasonic disperse 2h, the power of ultrasonic device is 150W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 60ml/min, dripping quantity is 60:1 according to receiving crystalline cellulose and graphene oxide mass ratio, continue ultrasonic disperse 1h and regulate pH to 7, obtain graphene oxide that concentration is 15.5mg/ml/receive crystalline cellulose dispersion liquid.
Graphene oxide/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 95 DEG C by d, be that 10:10 dropwise adds hydrazine hydrate according to the mass ratio of graphene oxide and hydrazine hydrate, 6h is reacted under mechanical agitation, stir speed (S.S.) is 1000r/min, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid.
The film through graphene/nano crystalline cellulose dispersion liquid obtained through Step d adopts the spin-coating method in existing technique to prepare graphene/nano crystalline cellulose hybridized film by e.After tested, the graphene/nano crystalline cellulose hybridized film of preparation at high temperature keeps dimensional stability, thermostability and electroconductibility good.
Claims (1)
1. film through graphene/nano crystalline cellulose dispersion liquid prepares a method for hybridized film, it is characterized in that: the described method preparing hybridized film is carried out according to the following steps:
The graphene oxide obtained after oxide treatment and crystalline cellulose of receiving add in dispersion agent by a respectively, compound concentration to be the graphene oxide dispersion of 0.1 ~ 1mg/ml and concentration be 5 ~ 20mg/ml receives crystalline cellulose dispersion liquid, ultrasonic disperse 1 ~ 2h, the power of ultrasonic device is 80 ~ 150W, then crystalline cellulose dispersion liquid of receiving dropwise adds in graphene oxide dispersion, rate of addition is 30 ~ 60ml/min, dripping quantity is 20 ~ 60:1 according to receiving crystalline cellulose dispersion liquid and graphene dispersing solution mass ratio, continue ultrasonic disperse 0.5 ~ 1h and regulate pH to 5 ~ 7, obtain graphene oxide that concentration is 1.5 ~ 15.5mg/ml/receive crystalline cellulose dispersion liquid,
Wherein, described graphene oxide diameter is 0.5 ~ 3 μm, and crystalline cellulose length of receiving is 0.5 ~ 1 μm, and diameter is 30 ~ 100nm;
Described dispersion agent is the mixing of one or more in deionized water or ethanol or ethylene glycol or propyl alcohol;
The graphene oxide obtained through a step/crystalline cellulose dispersion liquid of receiving is placed in the water bath with thermostatic control of 90 ~ 95 DEG C by b, be that 10:6 ~ 10 dropwise add reductive agent according to the mass ratio of graphene oxide dispersion and reductive agent, 4 ~ 6h is reacted under ultrasound condition, the power of ultrasonic device is 80 ~ 150w, is uniformly dispersed, stable film through graphene/nano crystalline cellulose dispersion liquid;
Wherein, described reductive agent is the one in hydrazine hydrate or quadrol or n-Butyl Amine 99 or sodium borohydride;
The film through graphene/nano crystalline cellulose dispersion liquid obtained through b step adopts spin-coating method or spraying method or casting filming therapy to prepare graphene/nano crystalline cellulose hybridized film by c.
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