CN108117068B - A kind of preparation method of graphene/nanometer microcrystalline cellulose aqueous dispersion liquid - Google Patents
A kind of preparation method of graphene/nanometer microcrystalline cellulose aqueous dispersion liquid Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of graphene/nanometer microcrystalline cellulose aqueous dispersion liquid.The dispersion A of certain solid content is made firstly, nano micro crystal cellulose is dispersed in water in the present invention；Meanwhile in water by graphene dispersion, the dispersion B of certain solid content is made.Then, dispersion A is dispersed in dispersion B, regulates and controls the additional proportion of nano micro crystal cellulose and graphene, regulation system pH to certain value obtains A/B water phase composite dispersion liquid.It is ultrasonically treated certain time under certain power finally, the A/B water phase composite dispersion liquid of acquisition is placed in ultrasonic cell disruptor, highly stable graphene/nanometer microcrystalline cellulose aqueous dispersion liquid is prepared.The present invention is based on electrostatic interaction, space steric effect and the associative mechanisms of ultrasonication to prepare high-stability graphene/nano micro crystal cellulose aqueous dispersion liquid；The present invention realizes synergistic effect, avoids simple technique superposition.
Description
Technical field
The invention belongs to graphene composite material fields, and in particular to a kind of graphene Aqueous dispersions of highly stable dispersion
The preparation method of liquid.
Background technique
Graphene possesses unique two-dimentional honeycomb lattice structure, is presently found most thin two dimensional crystal material,
Thickness is only 0.335 nm.Graphene has excellent electricity, mechanics and optically and mechanically property, graphene are unique and excellent
Performance, so that it can be widely applied to solar battery, supercapacitor, biological detection, display, fuel cell etc..
Improve graphene particle dispersibility can be greatly promoted in composite material strain, lead electrically and thermally transmit it is effective
The formation of network, to make graphene that there are outstanding potentiality in functional material production.However, due between graphene particle
There are very strong Van der Waals force, graphene sheet layer structure is easy to be condensed into graphene, this hinder significantly graphene into one
Step application.In this sense, how to realize the stable dispersion of graphene uniform with important in matrices of composite material
Realistic meaning.Generally believe that the dispersion of hydrophobicity graphene in an aqueous medium is a very big challenge at present, because it is essential
Film, coating or composite material above, which are further processed into, for graphene provides more possible applications.
For surface and the interfacial characteristics for making full use of graphene, it is necessary to adopt a series of measures, be at good, abundant
Dispersity.In film, coating or field of compound material, the dispersion of graphene and dispersion stabilization directly affect it and answer
Use performance.Therefore so that graphene is utilized effectively in film, coating or composite material, solve the dispersion of graphene
It is most important.
Currently, based on electrostatic interaction, space steric effect and the associative mechanism of ultrasonication prepare the graphene of high stable/
The research of nano micro crystal cellulose aqueous dispersion liquid, there is not been reported both at home and abroad.Physico-chemical property of the present invention from graphene itself
Start with, it is theoretical (dlvo theory) based on stably dispersing on the basis of understanding redox graphene reunion reason, dispersed
Property good graphene/nanometer microcrystalline cellulose aqueous dispersion liquid, be that graphene is special in film, coating or field of compound material
Change, functionalized application provide theoretical foundation and technical support, have important theory significance and practical significance.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of graphene/nanometer microcrystalline cellulose aqueous dispersion liquids
Preparation method.
The purpose of the present invention is what is be achieved through the following technical solutions:
Firstly, nano micro crystal cellulose is dispersed in water, the dispersion A of certain solid content is made；Meanwhile by graphite
Alkene is dispersed in water, and the dispersion B of certain solid content is made.Then, dispersion A is dispersed in dispersion B, is regulated and controled
The additional proportion of nano micro crystal cellulose and graphene, regulation system pH to certain value obtain A/B water phase composite dispersion liquid.With
Afterwards, the A/B water phase composite dispersion liquid of acquisition is placed in ultrasonic cell disruptor and is ultrasonically treated centainly under certain power
Highly stable graphene/nanometer microcrystalline cellulose aqueous dispersion liquid is prepared in time.
Furtherly, the solid content of the nano micro crystal cellulose Aqueous dispersions system A is 0.2~1.0%.
Furtherly, the pH of the nano micro crystal cellulose Aqueous dispersions system A is 6~7.
Furtherly, the nano micro crystal cellulose be 300~600 nanometers of length, 30~80 nanometers of width it is rodlike
Cellulose nanocrystal.
Furtherly, the solid content of the dispersion B is 0.5~2%.
Furtherly, the pH of the dispersion B is adjusted to 7~8.
Furtherly, the graphene of the dispersion B is redox graphene.
Furtherly, the pH of the A/B water phase composite dispersion liquid is adjusted to 6~7.
Furtherly, the additional proportion of the nano micro crystal cellulose is the 0~4% of graphene quality.
Furtherly, the ultrasonic power is 720W, sonication treatment time 5min.
Beneficial effects of the present invention:
(1), overall technology meets the theory of Green design using water as decentralized medium, also complies with environmentally friendly nanometer stone
The developing goal of ink material；
(2) electrostatic interaction, space steric effect and the synergistic effect of ultrasonication are played, it is difficult to be easily solved graphene water phase
With the critical issue of dispersion；
(3) simple production process, it is easy to operate, it achieves noticeable achievement；
(4) production process is safe and non-toxic, pollution-free.
Detailed description of the invention
Fig. 1 graphene suspension (a1, a2), nano micro crystal cellulose suspension (b1, b2) and graphene/nano
The TEM figure of rice microcrystalline cellulose aqueous dispersion liquid (c1, c2)；
The ultraviolet-visible absorption spectroscopy spectrogram of Fig. 2 graphene/nanometer microcrystalline cellulose aqueous dispersion liquid；
The sedimentation experiment electronic photo of Fig. 3 graphene/nanometer microcrystalline cellulose aqueous dispersion liquid.
Specific embodiment
The present invention will be further explained with reference to the examples below, but the scope of protection of present invention is not limited to
The range of embodiment expression.Unless otherwise indicated.
The principle of the present invention analysis: it for dispersion stabilization of the NCC in graphene aqueous phase system, can be managed according to DLVO
Resultant action potential energy U between particle inTTo be evaluated: UT=UA+UR+UHR+USTIn formula: UAFor model ylid bloom action potential energy, URFor
Effect of Electric Double Layer potential energy, UHRRepel potential energy, U for aquationSTFor steric hindrance potential energy.When NCC is dispersed in graphene aqueous phase system
In, the dispersion stabilization of suspended substance will depend on intergranular model ylid bloom action potential energy UA, Effect of Electric Double Layer potential energy UR, space bit
Hinder potential energy USTAnd aquation repels potential energy UHRThe sum of.UAIt is always attraction energy； URSize rely on particle surface potential value, and
The size of particle surface current potential depends on system pH； USTIt is related to the high molecular polymer in dispersion； UHRThen with
The hydrophilicrty on grain surface is closely related.
The present invention (is based on dlvo theory, NCC can be adsorbed on graphene by hydrogen bond action etc. by strengthening electrostatic interaction
On), space steric effect (NCC is chain macromolecule compound, there is certain molecule internal tension) and ultrasonication (ultrasonic wave with
A kind of form of energy acts on reactant, helps to improve reaction efficiency, have power is big, penetration power is strong, good directionality and
The advantages that cavitation, improves the repulsion potential energy between graphene particles), improve its dispersibility in water phase, stability, is graphite
Functionalized application of the alkene in film, coating or composite material lays the foundation.
Embodiment 1:
Firstly, nano micro crystal cellulose is dissolved in the water, regulation system pH to 6.5, solid content 0.2%, and persistently divide
20min is dissipated, dispersion A is obtained.Secondly, in water by certain graphene dispersion, the dispersion that solid content is 0.5% is made
System, regulation system pH to 7.5, and continue to disperse 20min, obtain dispersion B.Then, dispersion A is dispersed in dispersion
Be regulate and control in B nano micro crystal cellulose additional amount be graphene additional amount 0%, regulation system pH to 7.0 obtains A/B
Water phase composite dispersion liquid.Finally, the A/B water phase composite dispersion liquid of acquisition is placed in ultrasonic cell disruptor in power 720W
5~8min of lower ultrasonic treatment, sample ultrasonic environment are tepidarium.The above joint step is undergone, graphene aqueous dispersion liquid is obtained.
And it is analyzed and is compareed by TEM, ultraviolet-visible absorption spectroscopy, sedimentation experiment etc..As shown in figure, NCC can more uniformly
Ground is dispersed in graphene aqueous phase solution.Increase of the figure two with UV, visible light optical wavelength, the compound Aqueous dispersions of graphene/NCC
The absorbance of liquid is consequently increased, and further proves that NCC can improve dispersibility and stability of the graphene in water phase.From figure three
Sedimentation experiment electronic photo can be clear and intuitive find out increasing with NCC additional proportion, compound aqueous phase solution dispersion is more
It is uniform.
Embodiment 2:
Firstly, nano micro crystal cellulose is dissolved in the water, regulation system pH to 6.5, solid content 0.2%, and persistently divide
20min is dissipated, dispersion A is obtained.Secondly, in water by certain graphene dispersion, the dispersion that solid content is 0.5% is made
System, regulation system pH to 7.5, and continue to disperse 20min, obtain dispersion B.Then, dispersion A is dispersed in dispersion
Be regulate and control in B nano micro crystal cellulose additional amount be graphene additional amount 1%, regulation system pH to 7.0 obtains A/B
Water phase composite dispersion liquid.Finally, the A/B water phase composite dispersion liquid of acquisition is placed in ultrasonic cell disruptor in power 720W
5~8min of lower ultrasonic treatment, sample ultrasonic environment are tepidarium.The above joint step is undergone, it is fine to obtain graphene/nanometer crystallite
Tie up plain aqueous dispersion liquid.And it is analyzed and is compareed by TEM, ultraviolet-visible absorption spectroscopy, sedimentation experiment etc..As shown in Figure 1,
NCC can be more evenly dispersed in graphene aqueous phase solution.Increase of the Fig. 2 with UV, visible light optical wavelength, graphene/NCC
The absorbance of compound aqueous dispersion liquid is consequently increased, further prove NCC can improve graphene in water phase dispersibility and
Stability.From the sedimentation experiment electronic photo of figure three can be clear and intuitive find out increasing with NCC additional proportion, compound water phase
Solution disperses more uniform.
Embodiment 3:
Firstly, nano micro crystal cellulose is dissolved in the water, regulation system pH to 6.5, solid content 0.2%, and persistently divide
20min is dissipated, dispersion A is obtained.Secondly, in water by certain graphene dispersion, the dispersion that solid content is 0.5% is made
System, regulation system pH to 7.5, and continue to disperse 20min, obtain dispersion B.Then, dispersion A is dispersed in dispersion
Be regulate and control in B nano micro crystal cellulose additional amount be graphene additional amount 2%, regulation system pH to 7.0 obtains A/B
Water phase composite dispersion liquid.Finally, the A/B water phase composite dispersion liquid of acquisition is placed in ultrasonic cell disruptor in power 720W
5~8min of lower ultrasonic treatment, sample ultrasonic environment are tepidarium.The above joint step is undergone, it is fine to obtain graphene/nanometer crystallite
Tie up plain aqueous dispersion liquid.And it is analyzed and is compareed by TEM, ultraviolet-visible absorption spectroscopy, sedimentation experiment etc..Such as one institute of figure
Show, NCC can be more evenly dispersed in graphene aqueous phase solution.Figure two with UV, visible light optical wavelength increase, graphene/
The absorbance of the compound aqueous dispersion liquid of NCC is consequently increased, and further proves that NCC can improve dispersibility of the graphene in water phase
And stability.From the sedimentation experiment electronic photo of Fig. 3 can be clear and intuitive find out increasing with NCC additional proportion, Compound Water
Phase solution disperses more uniform.
Embodiment 4:
Firstly, nano micro crystal cellulose is dissolved in the water, regulation system pH to 6.5, solid content 0.2%, and persistently divide
20min is dissipated, dispersion A is obtained.Secondly, in water by certain graphene dispersion, the dispersion that solid content is 0.5% is made
System, regulation system pH to 7.5, and continue to disperse 20min, obtain dispersion B.Then, dispersion A is dispersed in dispersion
Be regulate and control in B nano micro crystal cellulose additional amount be graphene additional amount 3%, regulation system pH to 7.0 obtains A/B
Water phase composite dispersion liquid.Finally, the A/B water phase composite dispersion liquid of acquisition is placed in ultrasonic cell disruptor in power 720W
5~8min of lower ultrasonic treatment, sample ultrasonic environment are tepidarium.The above joint step is undergone, it is fine to obtain graphene/nanometer crystallite
Tie up plain aqueous dispersion liquid.And it is analyzed and is compareed by TEM, ultraviolet-visible absorption spectroscopy, sedimentation experiment etc..As shown in Figure 1,
NCC can be more evenly dispersed in graphene aqueous phase solution.Increase of the Fig. 2 with UV, visible light optical wavelength, graphene/NCC
The absorbance of compound aqueous dispersion liquid is consequently increased, further prove NCC can improve graphene in water phase dispersibility and
Stability.From the sedimentation experiment electronic photo of Fig. 3 can be clear and intuitive find out increasing with NCC additional proportion, compound water phase
Solution disperses more uniform.
Embodiment 5:
Firstly, nano micro crystal cellulose is dissolved in the water, regulation system pH to 6.5, solid content 0.2%, and persistently divide
20min is dissipated, dispersion A is obtained.Secondly, in water by certain graphene dispersion, the dispersion that solid content is 0.5% is made
System, regulation system pH to 7.5, and continue to disperse 20min, obtain dispersion B.Then, dispersion A is dispersed in dispersion
Be regulate and control in B nano micro crystal cellulose additional amount be graphene additional amount 4%, regulation system pH to 7.0 obtains A/B
Water phase composite dispersion liquid.Finally, the A/B water phase composite dispersion liquid of acquisition is placed in ultrasonic cell disruptor in power 720W
5~8min of lower ultrasonic treatment, sample ultrasonic environment are tepidarium.The above joint step is undergone, it is fine to obtain graphene/nanometer crystallite
Tie up plain aqueous dispersion liquid.And it is analyzed and is compareed by TEM, ultraviolet-visible absorption spectroscopy, sedimentation experiment etc..As shown in Figure 1,
NCC can be more evenly dispersed in graphene aqueous phase solution.Increase of the Fig. 2 with UV, visible light optical wavelength, graphene/NCC
The absorbance of compound aqueous dispersion liquid is consequently increased, further prove NCC can improve graphene in water phase dispersibility and
Stability.From the sedimentation experiment electronic photo of Fig. 3 can be clear and intuitive find out increasing with NCC additional proportion, compound water phase
Solution disperses more uniform.
It can be seen that original graphite alkene easily reunites in aqueous phase system, is difficult to disperse, received to lose to a certain extent
Meter Xiao Ying.And the method for the present invention is used, highly stable graphene/nanometer microcrystalline cellulose aqueous dispersion liquid can be made, this
Be conducive to the preparation and functionalized application of film, coating or composite material.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and example shown and described herein.
Claims (4)
1. a kind of preparation method of graphene/nanometer microcrystalline cellulose aqueous dispersion liquid, rich by nano micro crystal cellulose surface
Rich hydrophilic radical assigns graphene water phase moisture dispersibility；Electrostatic force, steric hindrance based on nano micro crystal cellulose
Effect improves graphene Aqueous dispersions stability, specifically:
Firstly, nano micro crystal cellulose is dispersed in water, the dispersion A of certain solid content is made；Meanwhile graphene being divided
It dissipates in water, the dispersion B of certain solid content is made；Secondly, dispersion A is dispersed in dispersion B, regulate and control nanometer
The additional proportion of microcrystalline cellulose and graphene, regulation system pH to certain value obtain A/B water phase composite dispersion liquid；Finally, will
The A/B water phase composite dispersion liquid of acquisition, which is placed in ultrasonic cell disruptor, is ultrasonically treated certain time under certain power,
Highly stable graphene/nanometer microcrystalline cellulose aqueous dispersion liquid is prepared；
The additional proportion of the nano micro crystal cellulose is the 1~4% of graphene quality；
The solid content of the nano micro crystal cellulose Aqueous dispersions system A is 0.2~1.0%；
The pH of the nano micro crystal cellulose Aqueous dispersions system A is 6~7；
The solid content of the dispersion B is 0.5~2%；
The pH of the dispersion B is adjusted to 7~8；
The pH of the A/B water phase composite dispersion liquid is adjusted to 6~7.
2. a kind of preparation method of graphene/nanometer microcrystalline cellulose aqueous dispersion liquid according to claim 1, feature
Be: the nano micro crystal cellulose is 300~600 nanometers of length, the rod-like fibre element of 30~80 nanometers of width is nanocrystalline.
3. a kind of preparation method of graphene/nanometer microcrystalline cellulose aqueous dispersion liquid according to claim 1, feature
Be: the graphene of the dispersion B is redox graphene.
4. a kind of preparation method of graphene/nanometer microcrystalline cellulose aqueous dispersion liquid according to claim 1, feature
Be: the ultrasonic power is 720W, sonication treatment time 5min.
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| 纳米微晶纤维素改性的石墨烯增强聚乙烯醇膜的研究;刘美华等;《南华大学学报（自然科学版）》;20170630;第31卷(第2期);第67-73页 * |
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