CN105218841B - It is a kind of by graphite to the simple preparation method of composite graphite alkene paper - Google Patents
It is a kind of by graphite to the simple preparation method of composite graphite alkene paper Download PDFInfo
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Abstract
The purpose of the present invention is to provide a kind of by graphite to the simple preparation method of composite graphite alkene paper, it is characterized by: graphite is added in nano-cellulose aqueous liquid dispersion, after carrying out mechanical stirring and ultrasonic treatment, obtain uniform and stable graphene/nanometer cellulose dispersion liquid, by being centrifugated out upper layer mixed liquor, composite graphite alkene paper is made after then falling moisture evaporation.This method is simple, it is at low cost, without complex device, environmental-friendly, can solve that graphene film forming existing in the prior art is poor, intensity is low, complex process and the problems such as environmental pollution.Good using the composite membrane mechanical strength and flexibility of this method preparation, size is controllable.
Description
Technical field
The invention belongs to graphenes and nano-cellulose application field, provide one kind especially with nano-cellulose and natural stone
Ink is that raw material is aided with the method that ultrasonic dispersion prepares graphene/nanometer cellulose composite material.
Background technique
Nano-cellulose be with rich cellulose-containing raw material (such as agricultural crop straw, wood type, crudefiber crop and shell),
The diameter obtained by technologies such as chemical hydrolysis, mechanically decoupled or biological enzymolysis is in several whiskers or threadiness to tens nanometers
Natural polymer nano material has the characteristics such as renewable, degradable, non-toxic and mechanical performance is excellent, in food, doctor
Medicine, beauty, electronic material and field of compound material have wide application prospect.Hydroxyl is rich in cellulose molecular chain, it is intermolecular
Easily hydrogen bond, thus nano-cellulose can form flexible transparent film.Compared with common high molecular materials matrix, its conduct is removed
Outside feature possessed by natural polymer, nano-cellulose film has lower thermal expansion coefficient, if composite membrane imparting is led
Flexible transparent conducting composite film can be obtained in charged particle, is expected to substitution conventional transparent conductive material and is widely applied.
Graphene is a kind of two-dimensional material for forming hexangle type in honeycomb lattice with sp2 hybridized orbit by carbon atom.Because of it
With excellent electricity, calorifics and mechanical property, it is expected in nano electron device, transparent conductive film, composite material, antistatic
The fields such as material, energy storage material and inductor are applied, thus become the novel carbon materials to attract attention after carbon nanotubes
Material.The special performance that graphene has makes it in the great application prospect of novel flexible field of electrical components, by nano-cellulose with
The compound preparation of graphene is of great significance for exploitation flexible electrode and energy storage material.
At present about nano-cellulose/graphene composite material research report mainly by graphene or the oxidation of reduction
The aqueous liquid dispersion of graphene and nano-cellulose is mixed to get composite membrane.The graphite oxide no matter selecting graphene or restoring
Alkene is directed to carry out graphite complicated processing method.Existing graphene generally passes through intercalation or stripping by raw material of graphite
The graphene powder (aggregation of ten layers or less graphene films) obtained from after, while being also related to during preparing graphene
The less graphene powder of the number of plies is obtained after removing/intercalated graphite after annealing expansion process.If selecting the graphite oxide of reduction
Alkene then needs first to aoxidize graphite strong oxidizer to increase graphite layers away from obtaining graphite oxide using ultrasonic wave aid dispersion
Then alkene mixed liquor is restored to obtain graphene with reducing agent.After graphene could be mixed with nano-cellulose in this way
Composite graphite alkene paper is prepared using the dispersion liquid of the available graphene/nanometer cellulose of ultrasonic dispersion.Therefore existing
Technical process is cumbersome, and the production cycle is long, the device is complicated, and production cost is expensive, and a large amount of chemistry are used in oxidation and reduction process
Reagent has pollution to environment.
The present invention is aided with mechanical stirring using nano-cellulose as dispersion liquid, ultrasonic wave disperses and centrifuge separation can be obtained
Graphene extrusion coating paper can be obtained by moisture evaporation in the dispersion liquid of graphene/nanometer cellulose.It is compared with the traditional method, it should
Method and process is simple, and production cost is low, and device simple is environmentally protective.
Summary of the invention
The purpose of the present invention is to provide a kind of by graphite to the simple preparation method of composite graphite alkene paper, using this method
The composite membrane mechanical strength and flexibility of preparation are good, and size is controllable.
The present invention specifically provides a kind of preparation method of composite graphite alkene paper, it is characterised in that: nanometer is added in graphite
In cellulose aqueous liquid dispersion, after carrying out mechanical stirring and ultrasonic treatment, uniform and stable graphene/nanometer cellulose point is obtained
Graphene and nano cellulose composite film is made by being centrifugated out upper layer mixed liquor in dispersion liquid after then falling moisture evaporation
(i.e. composite graphite alkene paper).
Nano-cellulose selected by the present invention is natural polymer, and content is more on earth for raw material, distribution is wide, raw material
It can be the wastes such as the wooden class, crudefiber crop, shell and the stalk of crops.Nano-cellulose good mechanical property (springform itself
Measure 150G Pa, tensile strength 6GPa), surface activity due to being rich in hydroxy functional group is big, and has renewable, degradable, nontoxic
The advantages that, it is environmental-friendly Preen nono material.The suspension of nano-cellulose in water to graphite play effective removing,
Dispersion, film forming and humidification, form complete membrane.It is good using the composite membrane mechanical strength and flexibility of this method preparation,
Size is controllable.
The preparation method of composite graphite alkene paper of the present invention, it is characterised in that: sonication treatment time 0.5-12h, if
Standby power is 100-1000W.
The preparation method of composite graphite alkene paper of the present invention, it is characterised in that: the nano-cellulose aqueous liquid dispersion
The concentration of middle nano-cellulose is 0.1-0.5wt.%, preparation method are as follows: nano-cellulose and water is added in conical flask,
Being aided with ultrasonic treatment 0.5-12h, plant capacity 100-1000W after stirring 0.5-12h at room temperature makes nano-cellulose Yu Shuizhong
It is fully dispersed.
The preparation method of composite graphite alkene paper of the present invention, it is characterised in that: to graphene/nanometer cellulose dispersion liquid
5-30min, revolving speed 5000-16000rpm is centrifuged.
The preparation method of composite graphite alkene paper of the present invention, it is characterised in that: the additive amount of graphite accounts for graphite and nanometer
The 0.1-95% of cellulose gross mass.
The preparation method of composite graphite alkene paper of the present invention, which is characterized in that specific preparation step are as follows:
1) nano-cellulose, is placed in conical flask and is added water, makes the concentration 0.1-0.5wt.% of nano-cellulose,
It is stirred at room temperature after 0.5-12h and is aided with ultrasonic treatment 0.5-12h, plant capacity 100-1000W and makes nano-cellulose in water
In it is fully dispersed, obtain the dispersion liquid of nano-cellulose in water at this time；
2) graphite, is added into nano-cellulose dispersion liquid, the additive amount of graphite accounts for graphite and nano-cellulose gross mass
0.1-95%, the mixed liquor of evenly dispersed nano-cellulose and graphene is obtained after stirring and ultrasonic treatment；Wherein
Ultrasonic treatment device therefor power is 100-1000W, handles 0.5-12h；
3) processing, is centrifuged with centrifuge in the dispersion liquid that step 2) obtains, handles 5-30min, revolving speed is
5000-16000rpm, the suspension for taking out upper layer are stand-by；(it can will weigh, pass through after the solid granulates for being deposited on bottom drying
Ultimate yield is calculated)；
4), the mixture of nano-cellulose and graphene is injected in culture dish, in room temperature or heating condition down toward moisture
After volatilization, the graphene and the complete composite membrane of nano-cellulose of compliant conductive can be obtained after film is taken off from culture dish.
The preparation method of composite graphite alkene paper of the present invention, it is characterised in that: heating temperature is not higher than in step 4)
100 degrees Celsius.
The present invention provides a kind of green technology of preparing of graphene/nanometer cellulose composite membrane, method is simple, cost
It is low, without complex device, environmental-friendly, can solve that graphene film forming existing in the prior art is poor, intensity is low, complex process
And the problems such as environmental pollution.Compared with prior art, the graphene composite film intensity obtained using this method is good, size can
Control.Nano-cellulose has mechanical performance excellent, renewable, degradable, avirulent excellent as natural polymer nano material
Point is that have receiving for broad prospect of application in fields such as food packaging, electronic product, biological medicine, beauty product, composite materials
Rice material.Since nano-cellulose mechanical strength and film light transmittance are high, flexibility is good, and thermal expansion coefficient is low, in following electronics
Great application prospect in device products, thus it is significant to develop its functional material.
Detailed description of the invention
Fig. 1 graphite in nano-cellulose dispersion liquid through the photo before and after mechanical stirring ultrasonic disperse, wherein (a), ultrasound
Before dispersion, the graphene and nano-cellulose mixed liquor that (b), after ultrasonic disperse obtain.
The transmission electron microscope photo and selective electron diffraction style of graphene after Fig. 2 removing.
The composite membrane of Fig. 3 graphene/nanometer cellulose.
The composite film surface stereoscan photograph of Fig. 4 graphene/nanometer cellulose.
The X ray diffracting spectrum of Fig. 5 graphene/nanometer cellulose composite membrane.
The differential thermal analysis curve of Fig. 6 graphene/nanometer cellulose composite membrane.
The Raman spectrum of Fig. 7 graphene/nanometer cellulose composite membrane.
Specific embodiment
Embodiment 1
Nano-cellulose is obtained by chemical hydrolysis flax fiber, the water containing 20g is added in 0.1g nano-cellulose powder
In conical flask, stir 0.5h after be ultrasonically treated 0.5h under the power of 800W, obtain the dispersion liquid of nano-cellulose, then plus
Enter 0.9g graphite, stir this mixed liquor and by mixed liquor under 100W power by ultrasonic treatment 12h to being uniformly dispersed (at ultrasound
Reason front and back photo is see Fig. 1), mixed liquor is then centrifuged 15min under the conditions of 10000rpm, upper layer dispersion liquid is poured slowly into
In culture dish, it is placed in dry in the drying box that temperature is 80 DEG C to moisture and all volatilizees, then take film i.e. from culture dish off
Can be obtained the composite membrane (see Fig. 3,4) of graphene/nanometer cellulose, Fig. 2 be after removing the transmission electron microscope photo of graphene and
Selective electron diffraction style, Fig. 5 are the X ray diffracting spectrum of graphene/nanometer cellulose composite membrane, and Fig. 6 is graphene/nanometer
The differential thermal analysis curve of cellulose composite membrane, Fig. 7 are the Raman spectrums of graphene/nanometer cellulose composite membrane.
Embodiment 2
Nano-cellulose is obtained by chemical hydrolysis wood pulp cellulose, the water containing 50g is added in 0.25g nano-cellulose powder
In conical flask, stir 0.5h after be ultrasonically treated 0.5h under the power of 800W, obtain the dispersion liquid of nano-cellulose, then plus
Enter 0.75g graphite, this mixed liquor is stirred and under 100W power by ultrasonic treatment 10h, then by mixed liquor in 5000rpm item
It is centrifuged 30min under part, upper layer dispersion liquid is poured slowly into culture dish, is placed in the drying box that temperature is 60 DEG C and dries to water
Divide all volatilizations, then taking film from culture dish off can be obtained graphene nano fiber element composite membrane.
Embodiment 3
Nano-cellulose is obtained by chemical hydrolysis shinyleaf yellowhorn fruit shell fiber, the addition of 0.5g nano-cellulose powder is contained
In the conical flask of 100g water, it is ultrasonically treated 12h under the power of 100W after stirring 12h, obtains the dispersion liquid of nano-cellulose,
Then be added 0.5g graphite, stir this mixed liquor and under 800W power by ultrasonic treatment 2h, then by mixed liquor carry out from
Heart separation (separation 5min, revolving speed 16000rpm), upper layer dispersion liquid is poured slowly into culture dish, being placed in temperature is 40 DEG C
It is dried in drying box to moisture and is all volatilized, then film taken off to that graphene/nanometer cellulose can be obtained is compound from culture dish
Film.
Embodiment 4
Nano-cellulose is obtained by chemical hydrolysis rice straw stalk fiber.The addition of 0.75g nano-cellulose powder is contained
In the conical flask of 450g water, it is ultrasonically treated 6h under the power of 200W after stirring 6h, obtains the dispersion liquid of nano-cellulose, so
0.25g powdered graphite is added afterwards, this mixed liquor is stirred and under 1000W power by ultrasonic treatment 0.5h, then by mixed liquor
It is centrifuged 10min in 14000rpm, upper layer dispersion liquid is poured into culture dish slowly, is placed in the drying box that temperature is 100 DEG C and does
It is dry all to volatilize to moisture, then film is taken off to the composite membrane that graphene/nanometer cellulose can be obtained from culture dish.
Embodiment 5
Nano-cellulose is obtained by chemical hydrolysis rice straw stalk fiber, water containing 450g is added in 0.9g nano-cellulose powder
Conical flask in, stir 6h after be ultrasonically treated 6h under the power of 100W, obtain the dispersion liquid of nano-cellulose, be then added
0.1g powdered graphite stirs this mixed liquor and under 1000W power by ultrasonic treatment 0.5h, then mixed liquor exists
13000rpm is centrifuged 15min, and upper layer dispersion liquid is poured slowly into culture dish, is placed in the drying box that temperature is 100 DEG C and does
It is dry all to volatilize to moisture, then film is taken off to the composite membrane that graphene/nanometer cellulose can be obtained from culture dish.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of preparation method of composite graphite alkene paper, it is characterised in that: nano-cellulose is obtained by chemical hydrolysis, by stone
Ink is added in nano-cellulose aqueous liquid dispersion, after carrying out mechanical stirring and ultrasonic treatment, obtains uniform and stable graphene/nano
Graphene and Nanowire is made by being centrifugated out upper layer mixed liquor in rice cellulose dispersion liquid after then falling moisture evaporation
Tie up plain composite membrane, i.e. composite graphite alkene paper；The additive amount of graphite accounts for the 75-95% of graphite Yu nano-cellulose gross mass；
The concentration of nano-cellulose is 0.1-0.5wt.%, preparation method in the nano-cellulose aqueous liquid dispersion are as follows: will
Nano-cellulose and water are added in conical flask, are aided with ultrasonic treatment 0.5-12h, plant capacity after 0.5-12h is stirred at room temperature
For 100-1000W, keep nano-cellulose fully dispersed in water.
2. according to the preparation method of composite graphite alkene paper described in claim 1, it is characterised in that: to graphene/nanometer cellulose
5-30min, revolving speed 5000-16000rpm is centrifuged in dispersion liquid.
3. according to the preparation method of composite graphite alkene paper described in claim 1, which is characterized in that specific preparation step are as follows:
1) nano-cellulose, is placed in conical flask and is added water, makes the concentration 0.1-0.5wt.% of nano-cellulose, in room
It is aided with ultrasonic treatment 0.5-12h, plant capacity 100-1000W after the lower stirring 0.5-12h of temperature, fills nano-cellulose Yu Shuizhong
Dispersion, obtains the dispersion liquid of nano-cellulose in water at this time；
2) graphite, is added into nano-cellulose dispersion liquid, the additive amount of graphite accounts for the 75- of graphite Yu nano-cellulose gross mass
95%, the mixed liquor of evenly dispersed nano-cellulose and graphene is obtained after stirring and ultrasonic treatment；Wherein at ultrasound
Reason device therefor power is 100-1000W, handles 0.5-12h；
3) processing, is centrifuged with centrifuge in the dispersion liquid that step 2) obtains, handles 5-30min, revolving speed 5000-
16000rpm, the suspension for taking out upper layer are stand-by；
4), the mixture of nano-cellulose and graphene is injected in culture dish, in room temperature or heating condition down toward moisture evaporation
Afterwards, the graphene and the complete composite membrane of nano-cellulose of compliant conductive can be obtained after film being taken off from culture dish.
4. according to the preparation method of composite graphite alkene paper described in claim 3, it is characterised in that: heating temperature is not in step 4)
Higher than 100 degrees Celsius.
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| CN105754146B (en) * | 2016-03-31 | 2019-05-14 | 华南理工大学 | A kind of nano-cellulose/two-dimensional material composite flame-proof material and preparation method thereof |
| CN105860143A (en) * | 2016-05-14 | 2016-08-17 | 上海大学 | Flexible nanocellulose-graphene composite membrane and preparation method thereof |
| CN106832425A (en) * | 2016-09-20 | 2017-06-13 | 济南圣泉集团股份有限公司 | High performance Graphene composite nano fiber element and preparation method thereof, application |
| CN109896522A (en) * | 2017-12-11 | 2019-06-18 | 山东省圣泉生物质石墨烯研究院 | A kind of graphene composite nano fiber element, preparation method and purposes |
| CN108130772A (en) * | 2017-12-23 | 2018-06-08 | 林荣铨 | A kind of method that anti-bacteria paper is prepared using graphene/shell |
| CN110092947B (en) * | 2018-01-30 | 2021-03-02 | 山东省圣泉生物质石墨烯研究院 | Micro-nano cellulose compound, and preparation method and application thereof |
| CN109942720A (en) * | 2019-03-29 | 2019-06-28 | 济南圣泉集团股份有限公司 | A kind of nano cellulose material and its preparation method and application |
| CN110408080A (en) * | 2019-08-13 | 2019-11-05 | 沈阳航空航天大学 | Graphene oxide and its composite nano fiber element conductive flexible film and its preparation method |
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| WO2013076372A1 (en) * | 2011-11-24 | 2013-05-30 | Teknologian Tutkimuskeskus Vtt | Nanocellulose composites |
| CN103937010A (en) * | 2014-04-28 | 2014-07-23 | 华南理工大学 | High-performance graphene/cellulose composite hydrogel and aerogel and preparation methods thereof |
| CN104627977A (en) * | 2013-11-07 | 2015-05-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide reinforced composite carbon nanopaper and production method thereof |
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| WO2013076372A1 (en) * | 2011-11-24 | 2013-05-30 | Teknologian Tutkimuskeskus Vtt | Nanocellulose composites |
| CN104627977A (en) * | 2013-11-07 | 2015-05-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide reinforced composite carbon nanopaper and production method thereof |
| CN103937010A (en) * | 2014-04-28 | 2014-07-23 | 华南理工大学 | High-performance graphene/cellulose composite hydrogel and aerogel and preparation methods thereof |
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