CN104261392A - Preparation method of borate ion crosslinked conductive graphene paper - Google Patents
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Abstract
The invention discloses a preparation method of borate ion crosslinked conductive graphene paper. The preparation method comprises the following steps: preparing graphite oxide by adopting an improved Hummers method and ultrasonically stripping in deionized water to obtain graphite oxide hydrosol; then, adding a sodium hydroxide solution into the graphite oxide hydrosol to adjust the pH to 10-12; then adding boric acid; heating to 80-90 DEG C under a stirring condition; insulating heat for 3-5 hours; then naturally cooling; separating; washing; ultrasonically dispersing in deionized water; and finally filtering by a millipore filter and self-assembling layer by layer to obtain the borate ion crosslinked conductive graphene paper. The preparation method disclosed by the invention is simple, convenient to operate and low in cost, does not need special equipment and is easy for batch production. The obtained graphene paper has an excellent conductive performance and possibly can be used as an ideal conductive material for optoelectronic devices.
Description
Technical field
The present invention relates to graphene paper technical field, be specifically related to the preparation method of the conductive graphene paper that a kind of borate ion is cross-linked.
Background technology
Graphene oxide is the derivative of the Graphene with monoatomic layer thickness, is often used as the presoma preparing Graphene, and recently because the character of himself uniqueness becomes one of current study hotspot.It is low that graphene oxide has production cost, easy large-scale production, very easily dissolves in water polar solvent, the characteristics such as fabulous processing characteristics; There is good mechanical property and chemical property simultaneously.In the face of graphene oxide and border all there are a large amount of oxygen-containing functional groups of covalent bonds, there is sp
2and sp
3hydbridized carbon atoms structure, can by controlling its size, shape and sp
2the relative proportion in hydridization region modulates its optico-electronic properties further, also by covalently or non-covalently modification, graphene oxide can be changed into optical, electrical active material; In addition, graphene oxide can also mix with other functional materialss 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 two-dimentional multifunctional graphite vinyl sill (as graphene film and graphene paper etc.) utilizing the graphene oxide thin slice of micro/nano level to build macro-scale causes the extensive research interest of scientific worker.But the excellent properties that the graphene-based material of macro-scale does not often possess the Graphene of micro-scale is the bottleneck of its widespread use of restriction, the conductivity of especially macroscopical graphene-based material.Numerous scientific workers have paid great efforts in order to the conductivity improving macroscopical grapheme material.At present, the preparation method of macroscopic view two-dimensional graphene sill mainly contains several as follows: 1. chemical Vapor deposition process, this method is generally to be substrate deposition carbon under the high temperature conditions with copper or to be that substrate dialysis carbon is to prepare single or multiple lift Graphene with nickel, product crystal property is good, conductivity is better, but need special equipment, cost is higher, practical application is subject to great restriction.2. graphene oxide layer assembly, these class methods usually with the standby micro/nano level graphene oxide sheet of Hummers legal system improved for raw material, membrane structure is prepared by evaporation self-assembly, the methods such as self-assembly, lift, spin coating of filtering, generally need the conductivity recovering grapheme material with chemical reducing agent (as hydrazine hydrate, citric acid, VITAMIN, sodium borohydride etc.) redox graphene, the use of toxic chemical or conductivity do not reach requirement and limit further application.In addition, can also reduce at high temperature hydrogenation gas under protection of inert gas, or direct heating reduction recovers conductivity, but heat may damage the integrity of membrane structure.3. Graphene or graphene oxide doped modify after assembling, generally needing high temperature and special equipment, conduction property can regulating and controlling, but not easily large-scale production, therefore practical application is restricted equally.4. lewis' acid crosslinking-oxidization Graphene assembling, by adding a certain amount of metal ion in the aqueous solution of graphene oxide, as Ca
2+, Mg
2+, Fe
3+or after molecules (as Dopamine HCL, quadrol, polyimide, polyvinylpyrrolidone) etc. are crosslinked, refilter assembling and form two-dimensional graphene sill, the mechanical property of this material has had significant enhancing, but conductivity does not still reach requirement.
Summary of the invention
The object of the invention is to provide the preparation method of the conductive graphene paper that a kind of borate ion is cross-linked, to solve the deficiencies in the prior art.
The present invention is by the following technical solutions:
A preparation method for the conductive graphene paper that borate ion is cross-linked, comprises the steps:
Step one, be carbon source with Graphite Powder 99, adopt the Hummers legal system improved for graphite oxide, and ultrasonic stripping obtain the graphene oxide water-sol in deionized water;
Step 2, step one prepare the graphene oxide water-sol in add sodium hydroxide solution regulate pH to 10 ~ 12, add boric acid afterwards, the mass ratio of boric acid and graphene oxide is 0.1 ~ 2:50, be heated to 80 ~ 90 DEG C under agitation, insulation 3 ~ 5h, rear naturally cooling, be separated, washing, ultrasonic disperse, in deionized water, obtains the redox graphene water-sol that homodisperse borate ion is crosslinked;
The redox graphene water-sol that step 3, borate ion step 2 prepared are cross-linked obtains the crosslinked conductive graphene paper of borate ion by filtering with microporous membrane LBL self-assembly, after naturally drying, strips down from millipore filtration.
Described in step one, the concentration of the graphene oxide water-sol is 2 ~ 5mg/mL.
The concentration of the redox graphene water-sol that borate ion described in step 2 is cross-linked is 1 ~ 5mg/mL.
Millipore filtration described in step 3 is mixed cellulose ester microporous membrane, and diameter is 50 ~ 80mm, and aperture is 0.22 μm or 0.45 μm.
Beneficial effect of the present invention:
1, relate to the heat-processed 80 ~ 90 DEG C time and the filtering with microporous membrane process under room temperature in the present invention, operating process is convenient and simple, easily controls, with low cost, is easy to scale production;
2, the present invention adds sodium hydroxide solution in graphene oxide colloidal sol can the pH value of regulator solution be not only 10 ~ 12, and can serve as reductive agent remove portion oxygen-containing functional group in heat-processed; Boric acid adds the borate ion formed in alkaline mixed solution and serves as linking agent, the defect existed in graphene oxide sheet is repaired by the crosslinked action between the oxygen-containing functional group above borate ion and graphene oxide, further removal oxygen-containing functional group, strengthens conductivity;
3, the conductivity obtaining the single-layer graphene that the conductivity of graphene paper and chemical Vapor deposition process are produced in the present invention is close, and conductivity is excellent, and this conductive graphene paper may 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, without the need to special equipment, and with low cost, easily mass-produced.The most important thing is that the conductivity of the single-layer graphene that the conductivity of the graphene paper obtained and chemical Vapor deposition process are produced is close, when impressed voltage is 2 volts, current value reaches 30 milliamperes.This conductive graphene paper may become the perfect electric conductor being applied to opto-electronic device.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope image of the graphene oxide of amplification 30000 times;
Fig. 2 is the transmission electron microscope image of the redox graphene that the borate ion of amplification 50000 times is cross-linked;
Fig. 3 is the scanning electron microscope image of the graphene paper of amplification 1000 times;
Fig. 4 is the scanning electron microscope image on the graphene paper surface of amplification 50000 times;
Fig. 5 is the scanning electron microscope image of the tangent plane of the graphene paper of amplification 5000 times;
Fig. 6 is the scanning electron microscope image of the tangent plane of the graphene paper of amplification 50000 times;
Fig. 7 is graphene paper optical photograph image;
Fig. 8 is graphene paper conducting performance test figure.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention done and further explain.The following example only for illustration of the present invention, but is not used for limiting practical range of the present invention.
A preparation method for the conductive graphene paper that borate ion is cross-linked, comprises the steps:
Step one, to be less than or equal to 50 μm of Graphite Powder 99s for carbon source, adopt the Hummers legal system improved for graphite oxide, and ultrasonic stripping obtains the graphene oxide water-sol that concentration is 2 ~ 5mg/mL in deionized water.
Step 2, step one prepare the graphene oxide water-sol in add sodium hydroxide solution regulate pH to 10 ~ 12, be that 0.1 ~ 2:50 adds boric acid by the mass ratio of boric acid and graphene oxide afterwards, 80 ~ 90 DEG C are heated under induction stirring condition, insulation 3 ~ 5h, rear naturally cooling, filters or centrifugation, and deionized water wash for several times, ultrasonic disperse is in deionized water, and obtaining pure homodisperse concentration is the crosslinked redox graphene water-sol of the borate ion of 1 ~ 5mg/mL.Sodium hydroxide not only can the pH value of regulator solution in mixing solutions, can also play reductive action, graphene oxide partial reduction in heat-processed simultaneously.The boric acid added forms borate in basic solution, borate in heat-processed as linking agent, the defect existed in graphene oxide sheet is repaired by the crosslinked action between the oxygen-containing functional group above borate ion and graphene oxide, further removal oxygen-containing functional group, strengthens conductivity.
The redox graphene water-sol that step 3, borate ion step 2 prepared are cross-linked by diameter be 50 ~ 80mm, aperture is that the mixed cellulose ester microporous membrane filter layer self-assembly of 0.22 μm or 0.45 μm obtains, naturally, after drying, strip down from millipore filtration.The volume of the water-sol of the redox graphene that the thickness of this conductive ink alkene paper can be cross-linked by the borate ion of controlled filter controls.
The concrete preparation process of the step one graphene oxide water-sol is as follows: under ice-water bath induction stirring condition, Graphite Powder 99 is added in the container filling SODIUMNITRATE and the concentrated sulfuric acid solution of mass concentration more than 98%, the mass ratio of Graphite Powder 99, SODIUMNITRATE, the vitriol oil is 2: 1 ~ 2: 85 ~ 90, add potassium permanganate again, the mass ratio of potassium permanganate and Graphite Powder 99 is 3 ~ 5: 1, after potassium permanganate adds completely, remove ice-water bath, stirred at ambient temperature reaction 1 ~ 3h; Then in the water-bath of 25 ~ 40 DEG C, reaction 20 ~ 40min is continued, and add deionized water under agitation, wherein, the mass ratio of deionized water and Graphite Powder 99 is 50 ~ 60: 1, control temperature is at 90 ~ 100 DEG C, after reaction 10 ~ 30min, then with deionized water dilution, form graphite oxide suspension liquid; Finally add the hydrogen peroxide that mass concentration is 30%, the potassium permanganate that reduction is residual, graphite oxide suspension liquid is made to become glassy yellow, this graphite oxide suspension liquid is filtered, obtain graphite oxide throw out, use deionized water wash graphite oxide, until the PH of the filtered water of washing graphite oxide is 6 ~ 8, afterwards in deionized water after ultrasonic stripping, purified by centrifugation and obtain the graphene oxide water-sol.
Embodiment 1
1, be that the Graphite Powder 99 of 30 μm is as carbon source using particle diameter, utilize the Hummers legal system of above-mentioned improvement for graphite oxide, and ultrasonic stripping forms the graphene oxide water-sol of homodisperse 3mg/mL in deionized water, as shown in Figure 1, the graphene oxide sheet purity obtained is higher, substantially be minority ply together, there is obvious corrugated structure.
2, get the graphene oxide water-sol 50mL of the 3mg/mL of above-mentioned preparation, add appropriate sodium hydroxide solution and regulate pH to 11, add 5mg boric acid afterwards, in stink cupboard induction stirring condition under be heated to 90 DEG C, insulation 5h, rear naturally cooling, centrifugation, deionized water wash 3 times, ultrasonicly again to disperse in deionized water, obtain the redox graphene water-sol that pure homodisperse 2mg/mL borate ion is crosslinked, as shown in Figure 2, can find out that redox graphene sheet that borate ion is cross-linked maintains the basic pattern of graphene oxide, but there is significantly crosslinked structure of repairing.
3, the redox graphene water-sol that the borate ion of the above-mentioned preparation of 50mL is crosslinked is got, by diameter be 80mm, aperture is that to obtain diameter be the crosslinked conductive graphene paper of the borate ion of 8cm for the mixed cellulose ester microporous membrane filter layer self-assembly of 0.45 μm, naturally, after drying, strip down from millipore filtration.
The scanning electronic microscope that the conductive graphene paper be cross-linked by the borate ion of preparation carries out surface and tangent plane characterizes.As can be seen from Fig. 3 and Fig. 4: the surface of whole graphene paper has borate ion to be cross-linked the structure of repairing, Fig. 5 and Fig. 6 shows that graphene paper has obvious laminate structure, illustrate by simple filtration operating process be easy to prepare graphene paper.
The conductive graphene paper that the borate ion of preparation is crosslinked carries out electricity performance measurement.Fig. 7 is its optical photograph, the four point probe system of Semiconductor Parameter Analyzer (KEITHLEY 4200-SCS) is utilized to carry out electricity performance measurement to it, as shown in Figure 8, when impressed voltage is 2 volts, current value reaches 30 milliamperes, the single-layer graphene that its conductivity is produced close to chemical Vapor deposition process.
Embodiment 2
1, using particle diameter be the Graphite Powder 99 of 50 μm as carbon source, utilize the Hummers legal system of above-mentioned improvement for graphite oxide, and ultrasonic stripping forms the graphene oxide water-sol of homodisperse 5mg/mL in deionized water.
2, the graphene oxide water-sol 50mL of the 5mg/mL of above-mentioned preparation is got, add appropriate sodium hydroxide solution and regulate pH to 12, add 10mg boric acid afterwards, in stink cupboard induction stirring condition under be heated to 90 DEG C, insulation 5h, rear naturally cooling, centrifugation, deionized water wash 3 times, ultrasonicly disperses in deionized water again, obtains the redox graphene water-sol that pure homodisperse 5mg/mL borate ion is crosslinked.
3, the redox graphene water-sol that the borate ion of the above-mentioned preparation of 50mL is crosslinked is got, by diameter be 80mm, aperture is that to obtain diameter be the crosslinked conductive graphene paper of the borate ion of 8cm for the mixed cellulose ester microporous membrane filter layer self-assembly of 0.45 μm, naturally, after drying, strip down from millipore filtration.
Embodiment 3
1, using particle diameter be the Graphite Powder 99 of 30 μm as carbon source, utilize the Hummers legal system of above-mentioned improvement for graphite oxide, and ultrasonic stripping forms the graphene oxide water-sol of homodisperse 2mg/mL in deionized water.
2, the graphene oxide water-sol 50mL of the 2mg/mL of above-mentioned preparation is got, add appropriate sodium hydroxide solution and regulate pH to 10, add 0.2mg boric acid afterwards, in stink cupboard induction stirring condition under be heated to 80 DEG C, insulation 3h, rear naturally cooling, filtering separation, deionized water wash 3 times, ultrasonicly disperses in deionized water again, obtains the redox graphene water-sol that pure homodisperse 1mg/mL borate ion is crosslinked.
3, the redox graphene water-sol that the borate ion of the above-mentioned preparation of 50mL is crosslinked is got, by diameter be 50mm, aperture is that to obtain diameter be the crosslinked conductive graphene paper of the borate ion of 5cm for the mixed cellulose ester microporous membrane filter layer self-assembly of 0.22 μm, naturally, after drying, strip down from millipore filtration.
Claims (4)
1. the preparation method of conductive graphene paper that is cross-linked of borate ion, is characterized in that, comprise the steps:
Step one, be carbon source with Graphite Powder 99, adopt the Hummers legal system improved for graphite oxide, and ultrasonic stripping obtain the graphene oxide water-sol in deionized water;
Step 2, step one prepare the graphene oxide water-sol in add sodium hydroxide solution regulate pH to 10 ~ 12, add boric acid afterwards, the mass ratio of boric acid and graphene oxide is 0.1 ~ 2:50, be heated to 80 ~ 90 DEG C under agitation, insulation 3 ~ 5h, rear naturally cooling, be separated, washing, ultrasonic disperse, in deionized water, obtains the redox graphene water-sol that homodisperse borate ion is crosslinked;
The redox graphene water-sol that step 3, borate ion step 2 prepared are cross-linked obtains the crosslinked conductive graphene paper of borate ion by filtering with microporous membrane LBL self-assembly, after naturally drying, strips down from millipore filtration.
2. the preparation method of conductive graphene paper that is cross-linked of borate ion according to claim 1, it is characterized in that, described in step one, the concentration of the graphene oxide water-sol is 2 ~ 5mg/mL.
3. the preparation method of conductive graphene paper that is cross-linked of borate ion according to claim 1, it is characterized in that, the concentration of the redox graphene water-sol that borate ion described in step 2 is cross-linked is 1 ~ 5mg/mL.
4. the preparation method of conductive graphene paper that is cross-linked of borate ion according to claim 1, it is characterized in that, millipore filtration described in step 3 is mixed cellulose ester microporous membrane, and diameter is 50 ~ 80mm, and aperture is 0.22 μm or 0.45 μm.
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| 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 |
| CN105460922A (en) * | 2015-11-29 | 2016-04-06 | 福建医科大学 | Partially reduced GO (graphene oxide) fluorescence resonance energy transfer nano-probe and preparation method thereof |
| CN106006615A (en) * | 2016-05-25 | 2016-10-12 | 哈尔滨工业大学 | Natural drying preparation method of graphene aerogel |
| CN106241784A (en) * | 2016-07-27 | 2016-12-21 | 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 hierarchy |
| CN106315563A (en) * | 2016-07-27 | 2017-01-11 | 中国科学院宁波材料技术与工程研究所 | Graphene material of ordered structure and preparing method thereof |
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| CN108439380A (en) * | 2018-06-08 | 2018-08-24 | 中国科学院城市环境研究所 | A kind of super-elasticity, the preparation method of super-hydrophobic pure graphene aerogel |
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