CN109704320A - Functional carbon material and preparation method thereof, dispersion liquid and its application - Google Patents
Functional carbon material and preparation method thereof, dispersion liquid and its application Download PDFInfo
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Abstract
The present invention provides functional carbon material and preparation method thereof, dispersion liquid and electrically conductive ink or battery conductive additives.Wherein, the preparation method of functional carbon material includes: that dry ball milling is carried out after mixing carbon material with high molecular polymer, to obtain the functional carbon material.This method is simple, convenient, it is easy to accomplish, it is at low cost, significant competitive advantage is provided for later industrialized production.
Description
Technical field
The present invention relates to field of material technology, specifically, be related to functional carbon material and preparation method thereof, dispersion liquid and its
Using.
Background technique
It is widely paid close attention to currently, preparing electrically conductive ink using carbon material.Wherein, graphene has its special physics
Performance, big theoretical specific surface area (2600m2/ g), heating conduction (3000W/ (mK)) outstanding and mechanical property
(1060GPa), and electron mobility (5000cm high at room temperature2/ (V.s)), special sp2 hydbridized carbon atoms arrangement group
At bi-dimensional cellular shape crystal structure, make it have the quantum hall effect of perfect quantum tunneling effect, half-integer.These are excellent
Different performance determines that it has great application prospect in electronics, biological medicine, information and energy field.However, graphene
Piece interlayer has stronger Van der Waals force, very easy to assemble, and makes that it is insoluble in water and there are commonly solvents, largely effects on
The performance of graphene performance in practical application, causes the performance for the electrically conductive ink being prepared using graphene poor.
Thus, current electrically conductive ink still has much room for improvement.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose be to propose it is a kind of it is simple, convenient, be easily achieved, at low cost or industrialized production has competitive advantage
Functional carbon material method.
In one aspect of the invention, the present invention provides a kind of methods for preparing functional carbon material.According to the present invention
Embodiment, this method comprises: dry ball milling is carried out after carbon material is mixed with high molecular polymer, to obtain the function
Carbon material can be changed.Inventors have found that this method is simple, convenient, it is easy to accomplish, carbon material can be made by dry ball milling
It is combined with each other between high molecular polymer by non-covalent bond, it is very efficient to the functional modification of carbon material, it is especially suitable
It is used to prepare hydrophily or lipophilic functional carbon material, so that obtained functional carbon material can uniformly, surely
Fixed is distributed in water or solvent, and can realize higher solid content, so as to efficient for preparing electrically conductive ink or electricity
Pond conductive additive, and the above method is at low cost, provides significant competitive advantage for industrialized production.
According to an embodiment of the invention, the carbon material is in graphene, active carbon, carbon nanotube, soft carbon and hard carbon
At least one.
According to an embodiment of the invention, the high molecular polymer has hydrophobic functional groups, the hydrophobic functional groups
Including at least one of ether and alkyl.
According to an embodiment of the invention, the high molecular polymer also has hydrophilic functional group, the hydrophily function
Group includes at least one of carboxyl and hydroxyl.
According to an embodiment of the invention, the high molecular polymer is selected from sodium carboxymethylcellulose (CMC), gardenia blue, second
At least one of base cellulose (EC) and carrotene.
According to an embodiment of the invention, by the carbon material and the high molecular polymer being 40:1- according to mass ratio
The ratio of 20:1 mixes.
According to an embodiment of the invention, the dry ball milling is carried out in planetary ball mill, the planetary ball mill
In abrasive material and the carbon material mass ratio be 40:1-20:1.
According to an embodiment of the invention, the revolving speed of the dry ball milling is 100rpm-400rpm, time 1h-3h.
According to an embodiment of the invention, after dry ball milling, further includes: the product for obtaining the dry ball milling is added
It is ultrasonically treated into solvent, obtains mixed solution；To the mixed solution carry out centrifugal treating, by the supernatant of acquisition into
Then row filtering is collected filter cake and is dried, obtains the functional carbon material.
According to an embodiment of the invention, the gross mass based on the functional carbon material, the high molecular polymer contains
Amount is 1wt%-2wt%.
According to an embodiment of the invention, the shape of the functional carbon material is sheet, and the functional carbon material
Having a size of 1 μm -30 μm.
In another aspect of this invention, the present invention provides a kind of functional carbon materials.According to an embodiment of the invention, should
Functional carbon material is prepared using mentioned-above method.Inventors have found that the functional carbon material can realize height
The preparation of the dispersion liquid of solid content, and solid content is higher by 2-3 times of general carbon material dispersion liquid in dispersion liquid.
In another aspect of this invention, the present invention provides a kind of dispersion liquids.According to an embodiment of the invention, the dispersion liquid
Including mentioned-above functional carbon material.Inventors have found that the solid content of the dispersion liquid is very high, mobility is strong, and electric conductivity is strong,
Particularly suitable for preparing the conductive additive in electrically conductive ink and battery.
According to an embodiment of the invention, the gross mass based on the dispersion liquid, the content of the functional carbon material can be high
Up to 25wt%.
In another aspect of this invention, the present invention provides a kind of electrically conductive ink or battery conductive additives.According to this hair
Bright embodiment, the electrically conductive ink or battery conductive additive include that mentioned-above functional carbon material either utilizes front
What the dispersion liquid was prepared.Inventors have found that the electric conductivity of the electrically conductive ink is strong, sheet resistance is low, is conducive to extensive
Production.
According to an embodiment of the invention, sheet resistance of electrically conductive ink when with a thickness of 30 microns can be down to 1.3 Ω/.
Detailed description of the invention
Fig. 1 is the high power SEM figure of the functional carbon material in embodiment 1.
Fig. 2 is the low power SEM figure of the functional carbon material in embodiment 1.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
The present invention is following understanding based on inventor and discovery and completes:
Currently, prepare there are mainly two types of the methods of carbon material dispersion liquid, a kind of method is by carbon material (such as graphite or swollen
Swollen graphite) it is applied directly in organic solvent or aqueous surfactant solution, one is prepared by the effect of ultrasonic wave, heating or air-flow
Determine the dispersion liquid of concentration.After solvent molecule or surfactant molecule are adsorbed on removing by pi-pi accumulation and hydrophobic effect etc.
Carbon material (such as graphene) surface, by electrostatic repulsion or intermolecular force, effective point of the carbon material after realizing removing
It dissipates；The lower problem of dispersion fluid solid content that is serious, obtaining that there are carbon material extent of exfoliation is low for this method, lamella is reunited；Have
The dispersion liquid of the available higher concentration of solvent, but it is at high cost, and its boiling point is higher, is not easy to remove, is unfavorable for dispersion liquid
Further apply.And another method is that covalent bond method is modified to carbon material progress surface, but this method is to the structure of carbon material
Destroy that bigger and complicated for operation, production cost is higher, while the solid content of dispersion liquid prepared at present is lower, generally
Lower than 5%.In view of the above technical problems, inventor conducts in-depth research, and finds after research, can be by polymer and carbon materials
Dry ball milling is carried out after material mixing, can effectively realize and the surface of carbon material is modified, without introducing solvent, solvent is not present
The big problem of separating difficulty, and this method is to carry out surface to carbon material using non-covalent bond method to be modified, and hardly destroys carbon
The structure of material, the solid content using the dispersion liquid of obtained functional carbon material preparation is high, and electric conductivity is strong, particularly suitable for preparation
Electrically conductive ink or battery conductive additive.
In view of this, in one aspect of the invention, the present invention provides a kind of methods for preparing functional carbon material.Root
According to the embodiment of the present invention, this method comprises: dry ball milling is carried out after carbon material is mixed with high molecular polymer, so as to
To the functional carbon material.Inventors have found that this method is simple, convenient, is easily achieved, can be made by dry ball milling
It obtains and is combined with each other between carbon material and high molecular polymer by non-covalent bond, it is very high to the functional modification of carbon material
Effect, and the structure of carbon material is hardly destroyed, without adding solvent, there is no the big problems of separating difficulty；It is particularly suitable for
Hydrophily and lipophilic functional carbon material are prepared, the functional carbon material dispersibility of acquisition is good, on functional carbon material
Compound high molecular polymer can prevent the irreversible reunion of carbon material, and then be contained using consolidating for its dispersion liquid being prepared
Amount is high；And the above method is at low cost, provides significant competitive advantage for later industrialized production.
According to an embodiment of the invention, the carbon material is in graphene, active carbon, carbon nanotube, soft carbon and hard carbon
At least one.Carbon material is from a wealth of sources as a result, and price is low, and the functionalized carbon of acquisition is surface modified to above-mentioned carbon material
The usage scenario of material is extensive, is conducive to large-scale production.
According to an embodiment of the invention, the high molecular polymer has hydrophobic functional groups, the hydrophobic functional groups
Including ether (containing-C-O-C- structure) and alkyl (such as chain, cricoid alkyl, dilute base, alkynyl, subunit, secondary base
At least one of Deng)；Specifically, above-mentioned hydrophobic functional groups can be with hydrophobic part agraphitic carbon in carbon material or big
The pi-conjugated system of π-is combined together with hydrophobic effect, as a result, with hydrophobic effect knot between above-mentioned high molecular polymer and carbon material
It is combined, the stable structure of the functional carbon material of acquisition, effectively improves the dispersibility of functional carbon material in a solvent, it is high
The presence of Molecularly Imprinted Polymer can prevent the irreversible reunion of carbon material, help to obtain the high dispersion liquid of solid content.
According to an embodiment of the invention, in order to further increase the dispersion effect of functional carbon material, high molecular polymer
On can also have functional group conducive to dispersion, for example, if functional carbon material is distributed in aqueous solvent, macromolecule
Polymerization can also have hydrophilic functional group, and the hydrophilic functional group includes at least one of carboxyl and hydroxyl；If will
Functional carbon material is distributed in nonaqueous solvents, then has hydrophobic functional groups on high molecular polymer, in ether and alkyl
At least one.The dispersion effect of functional carbon material in a solvent is more preferable as a result, and stability is more preferable, and can be realized higher
Solid content.
In some embodiments of the invention, in order to improve the structural stability and its in a solvent of functional carbon material
Dispersibility, the high molecular polymer in sodium carboxymethylcellulose, gardenia blue, ethyl cellulose and carrotene at least
It is a kind of.The structure of the modified functional carbon material obtained in surface is carried out more to carbon material using above-mentioned high molecular polymer as a result,
Add stabilization, dispersibility in a solvent more preferably, and can obtain hydrophily or lipophilic functional carbon material, application scenarios
Extensively, conducive to the consumption experience for meeting consumer.According to an embodiment of the invention, when high molecular polymer is selected from carboxymethyl cellulose
When sodium or gardenia blue, the functional carbon material being prepared has hydrophily, can be with higher solid content, stable dispersion
Into aqueous dispersion medium；When high molecular polymer is selected from ethyl cellulose or carrotene, the functionalization that is prepared
Carbon material has lipophilicity, can with higher solid content, stable be distributed in oiliness decentralized medium.Point obtained as a result,
The application scenarios of dispersion liquid are relatively broad, can satisfy the application demand in different systems.
According to an embodiment of the invention, according to mass ratio being 40:1-20 by the carbon material and the high molecular polymer:
The ratio of 1 (such as 40:1,35:1,30:1,25:1,20:1 etc.) mixes.The ratio of carbon material and high molecular polymer is closed as a result,
Suitable, the two composite effect is preferable, the functional carbon material obtained can either be made to have preferable dispersibility, and improve function
The yield for changing carbon material, if ratio is excessively high, can reduce the electric conductivity of functional carbon material relative to aforementioned proportion range,
If ratio is too low, the degree of modification of carbon material can be reduced, and cause the dispersion of functional carbon material unstable, reduce functionalization
The solid content and functional carbon material yield of carbon material dispersion liquid.
According to an embodiment of the invention, the dry ball milling is carried out in planetary ball mill.Pass through dry method ball as a result,
The hydrophobic end part of high molecular polymer can be in contact by mill with carbon material surface, and be combined together by hydrophobic effect.
In some embodiments of the invention, the mass ratio of the abrasive material in the planetary ball mill and the carbon material is 40:1-20:1
(such as 40:1,35:1,30:1,25:1,20:1 etc.).It is possible thereby to which pattern is constant before and after guaranteeing carbon material functionalization.Work as planet
When the mass ratio of abrasive material and the carbon material in ball mill is excessive, then it will lead to carbon material and irreversible reunion (such as graphite occur
Reunite between alkene lamella, form graphite-structure), when the mass ratio of abrasive material and the carbon material in planetary ball mill is too small, then
Contact of the macromolecule with carbon material is not enough, thus will affect the modification effect to carbon material.
According to an embodiment of the invention, the revolving speed of the dry ball milling be 100rpm-400rpm (such as 100rpm,
150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm etc.), the time is 1h-3h (such as 1h, 2h, 3h etc.).By
This, the revolving speed of dry ball milling and time are suitable, carbon material can be efficiently combined together with high molecular polymer, acquisition
The stable structure of functional carbon material.When the revolving speed of dry ball milling is excessive or overlong time, then it will lead to carbon material and occur not
Reversible reunion, when the revolving speed of dry ball milling is too small or the time is too short, then contact of the macromolecule with carbon material is not enough, thus
It will affect the modification effect to carbon material.
According to an embodiment of the invention, in functional carbon material, based on the gross mass of the functional carbon material, high score
The content of sub- polymer be 1wt%-2wt% (such as 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%,
1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2.0wt% etc.).High molecular polymer content is suitable as a result,
The dispersibility of functional carbon material in a solvent can be significantly improved, the dispersion liquid that solid content is high, electric conductivity is strong is help to obtain,
And then it help to obtain the good electrically conductive ink of electric conductivity.When the too high levels of high molecular polymer, then functionalization can be reduced
The electric conductivity of carbon material, when the content of high molecular polymer is too small, then the degree of modification of carbon material can reduce, to can reduce
The solid content and functional carbon material yield of functional carbon material dispersion liquid.
According to an embodiment of the invention, the shape of the functional carbon material is sheet, and the functional carbon material
Having a size of 1 μm -30 μm, such as 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm.The size of functional carbon material is closed as a result,
Suitable, dispersing uniformity is stronger in a solvent, is more advantageous to the electric conductivity of the solid content and dispersion liquid that improve dispersion liquid.It needs
Illustrate, the size of functional carbon material refers to the maximum value of line between any two points on the surface of laminated structure.
According to an embodiment of the invention, after dry ball milling, further includes: mix the product that dry ball milling obtains with solvent
Conjunction is ultrasonically treated, and mixed solution is obtained；Centrifugal treating is carried out to the mixed solution, the supernatant of acquisition was carried out
Then filter is collected filter cake and is dried, obtains the functional carbon material.The purity of the functional carbon material obtained as a result,
Height is more advantageous to and improves functional carbon material dispersion effect in a solvent, overcome functional carbon material dispersion it is uneven and
The unstable problem of slurry.It in some embodiments of the invention, will after completing above-mentioned dry ball milling in the ball mill
Ball milling product is added in the organic solvents such as water, ethyl alcohol or tetrahydrofuran, and ultrasound 10min-60min is (such as under ultrasonication
10min, 20min, 30min, 40min, 50min, 60min etc.), pass through centrifugation (revolving speed 4000rpm, centrifugation time 5min-
10min (such as 5min, 6min, 7min, 8min, 9min, 10min)) it removes and modifies bad carbon material, then again by supernatant
By vacuum filter, filter cake is collected, it is 24 hours dry 80 DEG C in vacuum drying oven, obtain functional carbon material.It needs to illustrate
Be, when high molecular polymer modification carbon material it is ineffective when, dispersion effect is bad in a solvent, be easy reunite, be centrifuged
Precipitating is formed in the process to be separated, and the dispersion effect of the relatively good carbon material of modification in a solvent is good, it is not easy to it is formed
It precipitates but is present in supernatant, therefore, functional carbon material can be effectively purified by above-mentioned centrifugally operated, so that finally
The service performance of the functional carbon material of acquisition is more preferably.
In another aspect of this invention, the present invention provides a kind of functions for electrically conductive ink or battery conductive additive
Change carbon material.According to an embodiment of the invention, the functional carbon material is prepared using mentioned-above method.Invention
People's discovery, which can realize the preparation of the dispersion liquid of high solids content, and in dispersion liquid solid content be higher by it is general
2-3 times of carbon material dispersion liquid.
In another aspect of this invention, the present invention provides a kind of dispersion liquids.According to an embodiment of the invention, the dispersion liquid
Including mentioned-above functional carbon material.Inventors have found that the solid content of the dispersion liquid is very high, electric conductivity is strong, mobile performance
By force, particularly suitable for the conductive additive for preparing electrically conductive ink or battery.
According to an embodiment of the invention, the step of preparing dispersion liquid can be as follows: according to a certain ratio by functionalized carbon
Material be added to ultrasound 30min-60min in solvent (such as water, ethyl alcohol or tetrahydrofuran etc.) (such as 30min, 40min, 50min,
60min etc.) stable dispersion liquid can be obtained.It is simple, convenient as a result, it is easy to accomplish.As previously mentioned, being based on functionalization carbon materials
The gross mass of material, high molecular polymer content be 1wt%-2wt% (such as 1wt%, 1.1wt%, 1.2wt%, 1.3wt%,
1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2.0wt% etc.), in this content range
It realizes the modification to carbon material, and obtains the stable dispersion liquid of various concentration, wherein the content when high molecular polymer is
When 1wt%, the dispersion liquid that solid content is 5wt% or so still can be obtained.
According to an embodiment of the invention, the gross mass based on the dispersion liquid, the content of the functional carbon material can be high
Up to 25wt% (such as 5wt%, 10wt%, 15wt%, 20wt%, 25wt% etc.).The content of functional carbon material is high as a result,
Electric conductivity is strong, and mobility is strong, and the electric conductivity for the electrically conductive ink being prepared is strong, better than the carbon materials using conventional method modification
Expect that (solid content of the dispersion liquid obtained using conventional method is more than that 5wt% will become basic later to the dispersion liquid being prepared
There is no mobility).
In another aspect of this invention, the present invention provides a kind of electrically conductive ink or battery conductive additives.According to this hair
Bright embodiment, the electrically conductive ink or battery conductive additive contain mentioned-above functional carbon material or utilize front
What the dispersion liquid was prepared.Inventors have found that the electric conductivity of the electrically conductive ink or battery conductive additive is strong, sheet resistance
It is low, be conducive to be mass produced, there is exploitation high conductivity water system or oil is the potentiality of electrically conductive ink.
According to an embodiment of the invention, the sheet resistance of the electrically conductive ink or battery conductive additive when with a thickness of 30 microns
It can be down to 1.3 Ω/.The sheet resistance of electrically conductive ink or battery conductive additive is low as a result, and electric conductivity is strong, and service performance is good.
Embodiments herein is described below in detail.
Embodiment
The conducting performance test method of dispersion liquid: about 4.5% (quality percentage is added in functional carbon material dispersion liquid
The solvent-based gross mass of content, which calculates, to be obtained) binder (such as acrylate or polyurethane etc.), then use spreader
The film on substrate (such as polyethylene terephthalate (PET) film etc.), at 80 DEG C after dry 12h, testing film
Sheet resistance, wherein film with a thickness of 30 microns.
Embodiment 1
The preparation of functional carbon material:
It weighs 4g graphene and 0.1gCMC is put into planetary ball mill, the mass ratio of the powder of zirconium oxide bead and addition is 20:
1, then zirconium oxide bead and ball milling product are added in 200ml water by planetary ball mill revolving speed 300rpm, runing time 1.5h,
Zirconium oxide bead is separated by strainer, the aqueous dispersions of acquisition carry out ultrasound 1h, then under conditions of revolving speed 4000rpm
10min is centrifuged to remove the functional carbon material of dispersion effect difference, supernatant is collected by vacuum filtration filter cake, filter cake is true
It is 24 hours dry 80 DEG C in empty baking oven, functional carbon material powder is obtained, the scanning electron microscope of obtained functional carbon material powder
Figure (SEM) is shown in Fig. 1 and Fig. 2, as can be seen that the graphene microstructure by modification is there is no changing from Fig. 1 and Fig. 2,
Still with the flake structure of silk shape, wherein polymer quality percentage composition is about 1.6% in the functional carbon material of acquisition
(being tested using thermogravimetric analysis, be calculated according to mass loss in heating process).
The preparation of dispersion liquid:
3g functional carbon material powder is weighed, is added it in the water of 97ml, ultrasonic disperse 2h can obtain stable water
Dispersion liquid, the solid content of dispersion liquid are 3wt%.
Embodiment 2-4
The preparation method is the same as that of Example 1 for functional carbon material and dispersion liquid in embodiment 2-4, the difference is that point
The solid content of dispersion liquid is different, and referring in particular to table 1, the conducting performance test of dispersion liquid the results are shown in Table 1 in embodiment 1-4.
Table 1
| Embodiment | Graphene/polymer polymer | Disperse fluid solid content | Acrylate | Thickness μm | Sheet resistance Ω/ |
| 1 | 40:1 | 3% | 4.5% | 30 | 143 |
| 2 | 40:1 | 6% | 4.5% | 30 | 68 |
| 3 | 40:1 | 9% | 4.5% | 30 | 3 |
| 4 | 40:1 | 15% | 4.5% | 30 | 1.3 |
The dispersion liquid that can be seen that high solids content from the test result of table 1 has lower sheet resistance, shows above-mentioned dispersion liquid
Potentiality to be exploited with products such as water system electrically conductive ink, battery conductive additives.
Embodiment 5
The preparation of functional carbon material:
It weighs 2g graphene and 0.1g ethyl cellulose is put into planetary ball mill, the mass ratio of zirconium oxide bead and graphene exists
Then the mixture of zirconium oxide bead and ball milling product is added to by 30:1, rotational speed of ball-mill 300rpm, runing time 1.5h
In 200ml ethyl alcohol, zirconium oxide bead is separated by strainer, the dispersion liquid of acquisition carries out ultrasound 1h, then in revolving speed
It is centrifuged 10min under conditions of 4000rpm to remove the functional carbon material of dispersion effect difference, supernatant is received by vacuum filter
Collect filter cake, filter cake is 24 hours dry 80 DEG C in vacuum drying oven, obtains functional carbon material powder, wherein the functionalization of acquisition
To be about 2% (tested, according to quality damage in heating process polymer quality percentage composition using thermogravimetry in carbon material
Mistake is calculated).
The preparation of dispersion liquid:
Appropriate functional carbon material powder is weighed, distributes it in ethyl alcohol or tetrahydrofuran or carbon tetrachloride, then surpasses
Sound disperses 1.5h, and stable dispersions can be obtained, wherein the solid content of dispersion liquid is 2wt%.
Embodiment 6-8
The preparation method of functional carbon material and dispersion liquid is with embodiment 5, the difference is that the solid content of dispersion liquid
Difference, referring in particular to table 2, the conducting performance test of dispersion liquid the results are shown in Table 2 in embodiment 5-8.
Table 2
| Embodiment | Graphene/polymer polymer | Disperse fluid solid content | Polyurethane | Thickness μm | Sheet resistance Ω/ |
| 1 | 20:1 | 2% | 4.5% | 30 | 210 |
| 2 | 20:1 | 4% | 4.5% | 30 | 90 |
| 3 | 20:1 | 9% | 4.5% | 30 | 3.8 |
| 4 | 20:1 | 17% | 4.5% | 30 | 2 |
The dispersion liquid that can be seen that high solids content from the data of table 2 has lower sheet resistance, should be the result shows that above-mentioned dispersion
Liquid just has the potentiality as highly conductive ink or battery conductive additive product.
Embodiment 9-10
The method of functional carbon material and dispersion liquid is prepared in the present embodiment with embodiment 1, the difference is that macromolecule
Polymer is gardenia blue, and the mass ratio of graphene and gardenia blue is 40:1, and the solid content of dispersion liquid is respectively 9% and 15%, tool
Body is referring to table 3.
Table 3
Embodiment 11-14
The method of functional carbon material and dispersion liquid is prepared in the present embodiment with embodiment 1, the difference is that carbon material
Mass ratio with CMC is difference 30:1 and 20:1, and the solid content of dispersion liquid is respectively 9% and 15%, referring in particular to table 4.
Table 4
| Embodiment | Graphene/polymer polymer | Disperse fluid solid content | Acrylate | Thickness μm | Sheet resistance Ω/ |
| 11 | 30:1 | 9% | 4.5% | 30 | 8 |
| 12 | 30:1 | 15% | 4.5% | 30 | 3.4 |
| 13 | 20:1 | 9% | 4.5% | 30 | 20 |
| 14 | 20:1 | 15% | 4.5% | 30 | 10.8 |
Embodiment 15
The method of functional carbon material and dispersion liquid is prepared in the present embodiment with embodiment 1, the difference is that carbon material
For active carbon, the solid content of dispersion liquid is respectively 10%.
Comparative example 1
(1) a certain amount of graphene powder is weighed, is added it in a certain amount of aqueous solution, is added using stirring, ultrasound
Work 2h, stirring rate 800r/min, supersonic frequency 40KHz, and 0.5h is dispersed by high-pressure homogeneous equipment, operating pressure is
Graphene just dispersion liquid is prepared in 15000psi.
(2) first dispersion liquid is sampled, is 1:100 by surfactant and graphene mass ratio, purchase is good for from Dongguan City
The anionic surfactant suspension dispersive agent QM-168 of row new material Science and Technology Ltd. is added to graphene just dispersion liquid
In, it is combined with stirring, ultrasound and is carried out further decentralized processing, stirring rate 800r/min, supersonic frequency 40KHz, place
Time 2h is managed, the stabilization aqueous dispersion of this graphene is finally prepared.
In this comparative example, solid content is more than after 3%, and product reforms into the very poor slurry of especially sticky mobility, can not
It is respectively 1% and 3% to solid content that dispersion liquid, which is formed, so can not obtain the dispersion liquid that solid content is more than 3% in the comparative example
Dispersion liquid conducting performance test the results are shown in Table 5.
Table 5
| Disperse fluid solid content | Acrylate | Thickness μm | Sheet resistance Ω/ |
| 1% | 4.5% | 30 | 1534 |
| 3% | 4.5% | 30 | 461 |
Comparative example 2
Take 1.0g graphene that the aqueous solution for filling the ethylene glycol diethyl ether diamines ferric acetate of 40-60ml 0.5mmol/L is added
In, first ultrasound 10min, the graphene dispersing solution tentatively dispersed in ultrasonic tank.
Dispersion liquid after above-mentioned ultrasound is heated, temperature controls between 60 DEG C -70 DEG C, carries out magnetic agitation, leads to
Cross the 30%H that 20ml is added dropwise in constant pressure funnel dropwise2O2Solution controls rate of addition, makes the temperature of solution at 75 DEG C or less.
Time for adding is dripped and subsequent continuous is kept stirring 1h in 60min or so.After the reaction was completed, obtained slurry with 0.45 μm
PTFE filter membrane, be filtered washing with 1L-2L distilled water, washing to no catalyst remains, and then sinks what is be collected by filtration
It forms sediment, 80 DEG C in vacuum drying oven, dry 24 hours, obtaining the functionalization graphene powder of hydroxyl modified, (i.e. Covalent bonding together was repaired
The functionalization graphene powder of decorations).
The preparation of dispersion liquid:
The graphene powder for weighing a certain amount of hydroxylating modification, adds it in a certain amount of aqueous solution, ultrasound point
2h is dissipated, the stable aqueous dispersions of different solid contents can be obtained, the solid content of the graphene powder of hydroxylating modification is more than 6%
Words, slurry does not have mobility, especially sticky, is respectively 1%, 3% and 6% dispersion liquid conducting performance test result to solid content
It is shown in Table 6.
Table 6
| Disperse fluid solid content | Acrylate | Thickness μm | Sheet resistance Ω/ |
| 1% | 4.5% | 30 | 963 |
| 3% | 4.5% | 30 | 235 |
| 6% | 4.5% | 30 | 168 |
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of method for preparing functional carbon material characterized by comprising
Dry ball milling is carried out after carbon material is mixed with high molecular polymer, to obtain the functional carbon material.
2. the method according to claim 1, wherein the carbon material is selected from graphene, active carbon, carbon nanometer
At least one of pipe, soft carbon and hard carbon.
3. the method according to claim 1, wherein the high molecular polymer has hydrophobic functional groups, institute
Stating hydrophobic functional groups includes at least one of ether and alkyl；
Optionally, the high molecular polymer also has hydrophilic functional group, and the hydrophilic functional group includes carboxyl and hydroxyl
At least one of；
Optionally, the high molecular polymer is in sodium carboxymethylcellulose, gardenia blue, ethyl cellulose and carrotene
It is at least one.
4. the method according to claim 1, wherein by the carbon material and the high molecular polymer according to matter
Amount is mixed than the ratio for being 40:1-20:1；
Optionally, the dry ball milling is carried out in planetary ball mill, the abrasive material in the planetary ball mill and the carbon
The mass ratio of material is 40:1-20:1；
Optionally, the revolving speed of the dry ball milling is 100rpm-400rpm, time 1h-3h.
5. the method according to claim 1, wherein after the dry ball milling, further includes:
The product that the dry ball milling obtains is mixed with solvent and is ultrasonically treated, mixed solution is obtained；
Centrifugal treating is carried out to the mixed solution, the supernatant of acquisition is filtered, then collect filter cake and is dried,
Obtain the functional carbon material；
Optionally, the gross mass based on the functional carbon material, the content of the high molecular polymer are 1wt%-2wt%.
6. the method according to claim 1, wherein the shape of the functional carbon material is sheet, and described
The size of functional carbon material is 1 μm -30 μm.
7. a kind of functional carbon material, which is characterized in that be prepared using the method for any of claims 1-6
's.
8. a kind of dispersion liquid, which is characterized in that including functional carbon material as claimed in claim 7.
9. dispersion liquid according to claim 8, which is characterized in that the gross mass based on the dispersion liquid, the functionalization
The content of carbon material may be up to 25wt%.
10. a kind of electrically conductive ink or battery conductive additive, which is characterized in that including functionalization carbon materials as claimed in claim 7
What material was either prepared using dispersion liquid described in claim 8 or 9；
Optionally, sheet resistance of electrically conductive ink when with a thickness of 30 microns can be down to 1.3 Ω/.
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