CN104261392B - A kind of preparation method of the conductive graphene paper of borate ion crosslinking - Google Patents
A kind of preparation method of the conductive graphene paper of borate ion crosslinking Download PDFInfo
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Abstract
The invention discloses the preparation method of the conductive graphene paper of a kind of borate ion crosslinking, use the Hummers method improved to prepare graphite oxide, and the most ultrasonic stripping obtains the graphene oxide hydrosol；Then, sodium hydroxide solution regulation pH to 10～12 is added in the graphene oxide hydrosol, add boric acid, under conditions of stirring, it is heated to 80～90 DEG C, is incubated 3～5h, rear natural cooling, separate, washing, ultrasonic disperse, in deionized water, obtains the graphene paper of borate ion crosslinking finally by filtering with microporous membrane LBL self-assembly.Preparation method of the present invention is simple, easy to operate, it is not necessary to special equipment and with low cost, easily produces in batches.The graphene paper obtained has excellent electric conductivity, and this conductive graphene paper is likely to become the perfect electric conductor being applied to opto-electronic device.
Description
Technical field
The present invention relates to graphene paper technical field, be specifically related to the system of the conductive graphene paper of a kind of borate ion crosslinking
Preparation Method.
Background technology
Graphene oxide is the derivant of the Graphene with monoatomic layer thickness, is often used as preparing the forerunner of Graphene
Body, and become one of current study hotspot due to the character of himself uniqueness recently.Graphene oxide has production cost
Low, easy large-scale production, easily dissolve in water polar solvent, the characteristic such as fabulous processing characteristics；Have good simultaneously
Mechanical performance and chemical property.The a large amount of oxygen-containing sense that covalent bond combines all is had in the face of graphene oxide and border
Group, has sp2And sp3Hydbridized carbon atoms structure, can be by controlling its size, shape and sp2Hydridization region relative
Ratio modulates its optico-electronic properties further, it is also possible to by covalently or non-covalently modification, graphene oxide is changed into
Optical, electrical active material；It addition, graphene oxide can also mix with other functional materials or compound thus obtain and have
Functional material free from worldly cares.
In order to realize the functionalized application of Graphene as early as possible, the graphene oxide thin slice of micro/nano level is utilized to build macro-scale
Two-dimentional multifunctional graphite vinyl sill (such as graphene film and graphene paper etc.) cause extensively grinding of scientific worker
Study carefully interest.But, the excellent properties of the Graphene that the graphene-based material of macro-scale does not the most possess micro-scale is system
About its wide variety of bottleneck, the electric conductivity of the most macroscopical graphene-based material.Numerous scientific workers are in order to improve
The electric conductivity of macroscopic view grapheme material has paid great efforts.At present, the preparation method of macroscopic view two-dimensional graphene sill
Mainly having the most several: 1. chemical vapour deposition technique, this method is usually under the high temperature conditions with copper for substrate deposition carbon
Or prepare single or multiple lift Graphene with nickel for substrate dialysis carbon, product crystal property is good, and electric conductivity is preferable, but needs
Wanting special equipment, relatively costly, actual application is extremely limited.2. graphene oxide layer assembly, this type of side
Method generally with the micro/nano level graphene oxide sheet prepared of Hummers method that improves as raw material, by evaporation self assembly,
The method such as self assembly, lifting, spin coating that filters prepares membrane structure, it is generally required to chemical reducing agent (as hydrazine hydrate,
Citric acid, vitamin, sodium borohydride etc.) redox graphene recover grapheme material electric conductivity, toxic chemical
The use of reagent or electric conductivity do not reach requirement and limit further application.Furthermore it is also possible to protect at noble gas
Protect the reduction of lower high-temperature hydrogenation gas, or directly heat reduction recovery electric conductivity, but high-temperature heating may damage membranaceous knot
The integrity of structure.3. Graphene or graphene oxide doped assemble after modifying, and are typically needing high temperature and special equipment,
Conduction property can control to adjust, but is difficult to large-scale production, and therefore actual application is similarly subjected to restriction.4. ion or
Molecule crosslinking-oxidization Graphene assembles, by adding a certain amount of metal ion in the aqueous solution of graphene oxide, as
Ca2+、Mg2+、Fe3+, or molecule (such as dopamine, ethylenediamine, polyimides, polyvinylpyrrolidone) etc. hands over
After connection, refiltering assembling and form two-dimensional graphene sill, the mechanical performance of this material has had significant enhancing, but
Electric conductivity still reaches to less than requiring.
Summary of the invention
It is an object of the present invention to provide the preparation method of the conductive graphene paper of a kind of borate ion crosslinking, to solve existing skill
The deficiency of art.
The present invention is by the following technical solutions:
The preparation method of the conductive graphene paper of a kind of borate ion crosslinking, comprises the steps:
Step one, with graphite powder as carbon source, use the Hummers method improved to prepare graphite oxide, and at deionized water
In ultrasonic stripping obtain the graphene oxide hydrosol；
Step 2, step one preparation the graphene oxide hydrosol in add sodium hydroxide solution regulation pH to 10～12,
The mass ratio adding boric acid, boric acid and graphene oxide afterwards is 0.1～2:50, is heated to 80～90 DEG C under agitation,
Insulation 3～5h, rear natural cooling, separate, washing, ultrasonic disperse, in deionized water, obtains homodisperse boric acid
The redox graphene hydrosol of radical ion crosslinking；
The redox graphene hydrosol of step 3, borate ion step 2 prepared crosslinking is by microporous filter membrane mistake
Filter LBL self-assembly obtains the conductive graphene paper of borate ion crosslinking, after naturally drying, under peeling off from microporous filter membrane
Come.
The concentration of the graphene oxide hydrosol described in step one is 2～5mg/mL.
Described in step 2, the concentration of the redox graphene hydrosol of borate ion crosslinking is 1～5mg/mL.
Microporous filter membrane described in step 3 is mixed cellulose ester microporous membrane, a diameter of 50～80mm, and aperture is 0.22 μm
Or 0.45 μm.
Beneficial effects of the present invention:
1, the present invention relates to the heating process when 80～90 DEG C and the filtering with microporous membrane process under room temperature, operated
Journey is convenient and simple, is easily controlled, with low cost, it is easy to large-scale production；
2, the present invention add in graphene oxide colloidal sol sodium hydroxide solution be possible not only to regulate solution pH value be 10～
12, and reducing agent can be served as in heating process and remove part oxygen-containing functional group；Boric acid adds shape in alkaline mixed solution
The borate ion become serves as cross-linking agent, by the friendship between the oxygen-containing functional group above borate ion and graphene oxide
Defect present in graphene oxide sheet is repaired in connection effect, removes oxygen-containing functional group further, strengthens electric conductivity；
3, the present invention obtains the electric conductivity of graphene paper and the conduction of the single-layer graphene of chemical vapour deposition technique production
Performance is close, and electric conductivity is excellent, and this conductive graphene paper is likely to become the perfect electric conductor being applied to opto-electronic device.
To sum up, preparation method of the present invention is simple, easy to operate, it is not necessary to special equipment and with low cost, easily criticizes
Amount produces.The most important thing is the single-layer graphene that the electric conductivity of graphene paper obtained produces with chemical vapour deposition technique
Electric conductivity is close, and when applied voltage is 2 volts, current value reaches 30 milliamperes.This conductive graphene paper is likely to become
It is applied to the perfect electric conductor of opto-electronic device.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope image of the graphene oxide amplifying 30000 times；
Fig. 2 is the transmission electron microscope image of the redox graphene of the borate ion crosslinking amplifying 50000 times；
Fig. 3 is the scanning electron microscope image of the graphene paper amplifying 1000 times；
Fig. 4 is the scanning electron microscope image on the graphene paper surface amplifying 50000 times；
Fig. 5 is the scanning electron microscope image of the tangent plane of the graphene paper amplifying 5000 times；
Fig. 6 is the scanning electron microscope image of the tangent plane of the graphene paper amplifying 50000 times；
Fig. 7 is graphene paper optical photograph image；
Fig. 8 is graphene paper conducting performance test figure.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing the present invention done and further explain.The following example is merely to illustrate this
Bright, but it is not used to limit the practical range of the present invention.
The preparation method of the conductive graphene paper of a kind of borate ion crosslinking, comprises the steps:
Step one, with the graphite powder less than or equal to 50 μm particle diameters as carbon source, use improve Hummers method prepare
Graphite oxide, and the most ultrasonic stripping obtains the graphene oxide hydrosol that concentration is 2～5mg/mL.
Step 2, step one preparation the graphene oxide hydrosol in add sodium hydroxide solution regulation pH to 10～12,
Afterwards by the mass ratio of boric acid and graphene oxide be 0.1～2:50 add boric acid, be heated under the conditions of electromagnetic agitation
80～90 DEG C, be incubated 3～5h, rear natural cooling, filter or centrifugation, deionized water wash for several times, ultrasonic disperse
In deionized water, obtain the reduction-oxidation of the borate ion crosslinking that pure homodisperse concentration is 1～5mg/mL
The Graphene hydrosol.Sodium hydroxide is possible not only to regulate the pH value of solution in mixed solution, in heating process the most also
Reduction can be played, graphene oxide partial reduction.The boric acid added forms borate, boron in alkaline solution
Hydrochlorate in heating process as cross-linking agent, between the oxygen-containing functional group above borate ion and graphene oxide
Defect present in graphene oxide sheet is repaired in crosslinked action, removes oxygen-containing functional group further, strengthens electric conductivity.
The redox graphene hydrosol of step 3, borate ion prepared by step 2 crosslinking by a diameter of 50～
80mm, aperture are that the mixed cellulose ester microporous membrane filter layer self assembly of 0.22 μm or 0.45 μm obtains, from
After so drying, strip down from microporous filter membrane.The borate that the thickness of this conductive ink alkene paper can be filtered by control from
The volume of the hydrosol of the redox graphene of son crosslinking controls.
The concrete preparation process of the step one graphene oxide hydrosol is as follows: under the conditions of ice-water bath electromagnetic agitation, by graphite
Powder adds and fills in the container of sodium nitrate and the mass concentration concentrated sulfuric acid solution more than 98%, graphite powder, sodium nitrate, dense
The mass ratio of sulphuric acid is 2: 1～2: 85～90, adds potassium permanganate, the mass ratio of potassium permanganate and graphite powder be 3～
5: 1, after potassium permanganate is added completely into, remove ice-water bath, stirring reaction 1～3h under room temperature；Then at 25～40 DEG C
Water-bath in continue reaction 20～40min, and add deionized water under agitation, wherein, deionized water and graphite
The mass ratio of powder is 50～60: 1, and control temperature, at 90～100 DEG C, after reaction 10～30min, then uses deionized water
Dilution, forms graphite oxide suspension；It is eventually adding the hydrogen peroxide that mass concentration is 30%, the potassium permanganate of reduction residual,
Make graphite oxide suspension become glassy yellow, this graphite oxide suspension is filtered, obtains graphite oxide precipitate, spend
Ionized water washing graphite oxide, until the pH crossing drainage of washing graphite oxide is 6～8, surpasses the most in deionized water
After sound is peeled off, purified by centrifugation and obtain the graphene oxide hydrosol.
Embodiment 1
1, using graphite powder that particle diameter is 30 μm as carbon source, the Hummers method of above-mentioned improvement is utilized to prepare graphite oxide,
And the most ultrasonic peel off formed homodisperse 3mg/mL the graphene oxide hydrosol, as it is shown in figure 1,
The graphene oxide sheet purity obtained is higher, and substantially minority ply is together, has obvious corrugated structure.
2, take the graphene oxide hydrosol 50mL of the 3mg/mL of above-mentioned preparation, add the regulation of appropriate sodium hydroxide solution
PH to 11, adds 5mg boric acid afterwards, is heated to 90 DEG C in fume hood under conditions of electromagnetic agitation, be incubated 5h,
Rear natural cooling, centrifugation, deionized water wash 3 times, ultrasonic again disperse in deionized water, obtain pure all
The redox graphene hydrosol of even scattered 2mg/mL borate ion crosslinking, as shown in Figure 2, it can be seen that boron
The redox graphene sheet of acid ion crosslinking maintains the basic pattern of graphene oxide, but has significantly crosslinking
The structure repaired.
3, the redox graphene hydrosol of the borate ion crosslinking of the above-mentioned preparation of 50mL is taken, by a diameter of
80mm, aperture are the boron that the mixed cellulose ester microporous membrane filter layer self assembly of 0.45 μm obtains a diameter of 8cm
The conductive graphene paper of acid ion crosslinking, after naturally drying, strips down from microporous filter membrane.
The scanning electron microscope that the conductive graphene paper that the borate ion of preparation cross-links carries out surface and tangent plane characterizes.
From Fig. 3 and Fig. 4 it can be seen that there are the structure of borate ion crosslinking repairing, Fig. 5 and Tu in the surface of whole graphene paper
6 show that graphene paper has obvious layer structure, illustrate to be easy to prepare graphene paper by simple filtration operating process.
The conductive graphene paper that the borate ion of preparation cross-links is carried out electricity performance measurement.Fig. 7 is its optical photograph,
Four probe systems utilizing Semiconductor Parameter Analyzer (KEITHLEY 4200-SCS) carry out electricity performance measurement to it,
As shown in Figure 8, when applied voltage is 2 volts, current value reaches 30 milliamperes, and its electric conductivity sinks close to chemical gaseous phase
The single-layer graphene that area method produces.
Embodiment 2
1, using graphite powder that particle diameter is 50 μm as carbon source, the Hummers method of above-mentioned improvement is utilized to prepare graphite oxide,
And the most ultrasonic peel off formed homodisperse 5mg/mL the graphene oxide hydrosol.
2, take the graphene oxide hydrosol 50mL of the 5mg/mL of above-mentioned preparation, add the regulation of appropriate sodium hydroxide solution
PH to 12, adds 10mg boric acid afterwards, is heated to 90 DEG C in fume hood under conditions of electromagnetic agitation, be incubated 5h,
Rear natural cooling, centrifugation, deionized water wash 3 times, ultrasonic again disperse in deionized water, obtain pure all
The redox graphene hydrosol of even scattered 5mg/mL borate ion crosslinking.
3, the redox graphene hydrosol of the borate ion crosslinking of the above-mentioned preparation of 50mL is taken, by a diameter of
80mm, aperture are the boron that the mixed cellulose ester microporous membrane filter layer self assembly of 0.45 μm obtains a diameter of 8cm
The conductive graphene paper of acid ion crosslinking, after naturally drying, strips down from microporous filter membrane.
Embodiment 3
1, using graphite powder that particle diameter is 30 μm as carbon source, the Hummers method of above-mentioned improvement is utilized to prepare graphite oxide,
And the most ultrasonic peel off formed homodisperse 2mg/mL the graphene oxide hydrosol.
2, take the graphene oxide hydrosol 50mL of the 2mg/mL of above-mentioned preparation, add the regulation of appropriate sodium hydroxide solution
PH to 10, adds 0.2mg boric acid afterwards, is heated to 80 DEG C in fume hood under conditions of electromagnetic agitation, be incubated 3h,
Rear natural cooling, filters and separates, and deionized water wash 3 times ultrasonic disperses in deionized water again, obtain pure uniformly
The redox graphene hydrosol of scattered 1mg/mL borate ion crosslinking.
3, the redox graphene hydrosol of the borate ion crosslinking of the above-mentioned preparation of 50mL is taken, by a diameter of
50mm, aperture are the boron that the mixed cellulose ester microporous membrane filter layer self assembly of 0.22 μm obtains a diameter of 5cm
The conductive graphene paper of acid ion crosslinking, after naturally drying, strips down from microporous filter membrane.
Claims (4)
1. the preparation method of the conductive graphene paper of a borate ion crosslinking, it is characterised in that comprise the steps:
Step one, with graphite powder as carbon source, use the Hummers method improved to prepare graphite oxide, and at deionized water
In ultrasonic stripping obtain the graphene oxide hydrosol；
Step 2, step one preparation the graphene oxide hydrosol in add sodium hydroxide solution regulation pH to 10～12,
The mass ratio adding boric acid, boric acid and graphene oxide afterwards is 0.1～2:50, is heated to 80～90 DEG C under agitation,
Insulation 3～5h, rear natural cooling, separate, washing, ultrasonic disperse, in deionized water, obtains homodisperse boric acid
The redox graphene hydrosol of radical ion crosslinking；
The redox graphene hydrosol of step 3, borate ion step 2 prepared crosslinking is by microporous filter membrane mistake
Filter LBL self-assembly obtains the conductive graphene paper of borate ion crosslinking, after naturally drying, under peeling off from microporous filter membrane
Come.
The preparation method of the conductive graphene paper of borate ion the most according to claim 1 crosslinking, its feature exists
In, the concentration of the graphene oxide hydrosol described in step one is 2～5mg/mL.
The preparation method of the conductive graphene paper of borate ion the most according to claim 1 crosslinking, its feature exists
In, described in step 2, the concentration of the redox graphene hydrosol of borate ion crosslinking is 1～5mg/mL.
The preparation method of the conductive graphene paper of borate ion the most according to claim 1 crosslinking, its feature exists
In, microporous filter membrane described in step 3 is mixed cellulose ester microporous membrane, a diameter of 50～80mm, and aperture is 0.22 μ
M or 0.45 μm.
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| CN104743549B (en) * | 2015-03-18 | 2017-01-11 | 浙江大学 | Non-layered cross-linked graphene oxide film as well as preparation method and application thereof |
| CN105047955A (en) * | 2015-05-28 | 2015-11-11 | 东南大学 | Preparation method of carbon paper coating for fuel cell based on layer-by-layer self-assembly technique |
| CN105460922B (en) * | 2015-11-29 | 2017-10-20 | 福建医科大学 | Partial reduction graphene oxide FRET nano-probe and preparation method thereof |
| CN106006615B (en) * | 2016-05-25 | 2018-04-06 | 哈尔滨工业大学 | A kind of graphene aerogel spontaneously dries preparation method |
| CN106315563B (en) * | 2016-07-27 | 2019-02-19 | 中国科学院宁波材料技术与工程研究所 | A kind of grapheme material of ordered structure and preparation method thereof |
| CN106241784B (en) * | 2016-07-27 | 2019-03-15 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the grapheme material of multilevel structure |
| CN108439380B (en) * | 2018-06-08 | 2021-03-09 | 中国科学院城市环境研究所 | Preparation method of super-elastic and super-hydrophobic pure graphene aerogel |
| CN111058078B (en) * | 2019-12-30 | 2021-09-24 | 中国科学院青海盐湖研究所 | Copper foil with graphene film coated on surface and preparation method thereof |
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