CN107814390A - A kind of grapheme material combined mica, preparation method and purposes - Google Patents
A kind of grapheme material combined mica, preparation method and purposes Download PDFInfo
- Publication number
- CN107814390A CN107814390A CN201711059856.6A CN201711059856A CN107814390A CN 107814390 A CN107814390 A CN 107814390A CN 201711059856 A CN201711059856 A CN 201711059856A CN 107814390 A CN107814390 A CN 107814390A
- Authority
- CN
- China
- Prior art keywords
- mica
- grapheme material
- graphene
- combined mica
- dispersion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/42—Micas ; Interstratified clay-mica products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The present invention relates to a kind of method of grapheme material combined mica, methods described comprises the following steps：(1) mica is dipped in oxidizing solution and pre-processed；(2) mica that step (1) pre-processes is mixed with grapheme material dispersion liquid, is modified processing, obtains grapheme material combined mica dispersion liquid.The preparation method of the grapheme material combined mica provided in the present invention can be by grapheme material and mica strong bonded, and grapheme material can be made to be adsorbed among the sheet surfaces or lamella of mica, realize the dispersed of grapheme material and the strong bonded with inorganic material；Easy to operate and condition is easily-controllable, the process time is short, high to the modification efficiency of mica；On the premise of identical graphene is added, higher electric conductivity can be obtained.
Description
Technical field
The invention belongs to inorganic material-modified field, is related to a kind of modified micaceous, preparation method and purposes, more particularly to one
Plant modified micaceous graphene, preparation method and purposes.
Background technology
Due to the extensive use of electronic instrument, work and life to people bring great convenience.Electromagnetic wave simultaneously
Interference also bring negative effect, and outside radiated electromagnetic wave can make its information leakage in itself due to instrument.So in order to
Solve this problem, electromagnetic wave must just be shielded.Main at present is exactly by the way that doping type electrically-conducting paint is coated into modeling
Material shell body, makes it conductive and then electromagnetic shielding effect, wherein nickel-base conducting paint (compared to silver) cost is relatively low, shielding effect
Fruit is moderate, it is easy to accomplish coating processes, occupies the staple market of electromagnetic screen coating.But because nickel powder is than great, in coating
In easily settle, easy caking is not easy redisperse afterwards, and extremely unfavorable to workmen's safety.And Conductive mica has proportion
Small, electrical conductivity is high, glossy, and abundant raw material is cheap, becomes the ideal material instead of nickel powder.In addition, lead
Electric mica surface coats light metal oxide, and resistivity is relatively large as conductive filler to be used for any anti-static material
In, the most commonly used is for coating, rubber, plastics.It can be used alone, can also mix make with other conductive fillers
With.
Graphene has high electron mobility, resistivity only has about 10 as a kind of new two-dimension nano materials-6
Ω cm, to be also most thin, most hard, the nano material of high heat conduction.It will will be carried in the layer graphene of mica powder Surface coating one
The electric conductivity of high mica powder, and can accomplish that electric conductivity is controllable by adjusting the content of graphene.
But directly by graphene coated in mica surface, with reference to insecure, the raising unobvious to mica conductive, this
Field need to develop a kind of surface can strong bonded grapheme material, there is electric conductivity the grapheme material being obviously improved to change
Property mica.
The content of the invention
In view of the shortcomings of the prior art, an object of the present invention is to provide a kind of side of grapheme material combined mica
Method, methods described comprise the following steps：
(1) mica is dipped in oxidizing solution and pre-processed；
(2) mica that step (1) pre-processes is mixed with grapheme material dispersion liquid, is modified processing, obtains graphite
Alkene Material cladding mica dispersion liquid.
Alternatively, the grapheme material combined mica dispersion liquid that step (2 ') obtains step (2) is carried out after step (2)
Filtering, dry, obtain grapheme material combined mica.
The present invention is pre-processed by the way that mica is placed in oxidizing solution so that its sheet surfaces or lamella and lamella
Between produce reactive species (such as hydroxyl, carboxyl), it is mixed and modified with grapheme material dispersion liquid afterwards, in modifying process
The reactive species of mica splittings and the SP2 keys of grapheme material, the deriveding group (such as hydroxyl, carboxyl, amino) contained
With reference to having obtained the compound mica of grapheme material.
For step (2 '), whether it is carried out, and depending on the shape of object, is answered when needing to prepare powdered graphite alkene material
When closing mica, it can select to carry out step (2 ')；When needing to prepare the dispersion liquid of grapheme material combined mica, can not enter
Row step (2 ')；When needing to prepare the dispersion liquid of grapheme material combined mica, after step (2 ') can also being carried out, by powdery
Grapheme material combined mica is dispersed again in dispersion liquid.
Preferably, the oxidizing solution is the mixed solution of the concentrated sulfuric acid and hydrogen peroxide.
From the mixed solution of the concentrated sulfuric acid and hydrogen peroxide as oxidizing solution, the two collaboration, can more efficiently exist
Generation reactive species (such as hydroxyl, carboxyl, carbonyl) inside mica splittings.
98% concentrated sulfuric acid that the concentrated sulfuric acid is well known to those skilled in the art.
Preferably, in the oxidizing solution, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 2~5:1, such as 3:1、4:1 etc.,
It is preferred that 7~9:3, wherein hydrogen peroxide concentration is based on 30v%.
Preferably, the temperature of the pretreatment be 70~110 DEG C, such as 72 DEG C, 74 DEG C, 77 DEG C, 79 DEG C, 82 DEG C, 86 DEG C,
89 DEG C, 92 DEG C, 96 DEG C, 99 DEG C, 102 DEG C, preferably 106 DEG C, 109 DEG C etc., 80~90 DEG C.
Preferably, the time of the pretreatment is 10~120min, for example, 13min, 18min, 23min, 28min,
33min、38min、43min、48min、53min、58min、63min、68min、73min、78min、83min、88min、
93min, 98min, 103min, 108min, 113min, 118min etc., preferably 40~70min.
Preferably, the grapheme material includes the material with graphene film Rotating fields, including single-layer graphene, bilayer
Any a kind or at least two kinds of of combination in graphene, multi-layer graphene, graphene oxide and Graphene derivative, is preferably aoxidized
Graphene and/or Graphene derivative, further preferred graphene oxide.
Preferably, the particle diameter of the mica is 2 μm~2mm, for example, 3 μm, 9 μm, 15 μm, 30 μm, 50 μm, 70 μm, 90 μm,
110 μm, 150 μm, 210 μm, 350 μm, 410 μm, 550 μm, 610 μm, 750 μm, 810 μm, 950 μm etc..
Preferably, the dispersant of the grapheme material dispersion liquid is hydrophilic solution, preferably includes water, can appoint with water
Any a kind or at least two kinds of of combination in the organic solvent of meaning ratio mixing.
Hydrophilic solution of the present invention is it can be appreciated that hydrophilic liquid, hydrophilic dispersion liquid, hydrophilic solvent etc..
Exemplarily, the organic solvent that can be mixed with water arbitrary proportion includes ethanol, acetone, methanol, tetrahydrochysene furan
Mutter, DMF, DMA, DMSO, hexamethyl phosphoramide, fourth sulfone, dioxane, hydracrylic acid, ethamine, ethylenediamine, glycerine, diethylene glycol (DEG) two
Methyl ether, 1, any a kind or at least two kinds of of combination in 3-dioxolane, pyridine.
The present invention is not specifically limited for the concentration of the grapheme material dispersion liquid, and exemplary can be 1~
10mg/g, such as 2mg/g, 3mg/g, 4mg/g, 5mg/g, 6mg/g, 7mg/g, 8mg/g, 9mg/g.
Preferably, the mixed proportion of the grapheme material and mica is 0.5~50:100, such as 0.6:100、0.9:
100、2:100、8:100、12:100、18:100、22:100、28:100、32:100、38:100、42:100、48:100 etc., it is excellent
Select 1~20:100.
Preferably, during the modification, it is stirred and is ultrasonically treated.
Preferably, the ultrasonic power is 1000~3000kW, such as 1.5kW, 2.0kW, 2.5kW etc..
Preferably, the stir speed (S.S.) be 800~3000 turns, such as 900 turns, 1200 turns, 1500 turns, 1900 turns, 2200
Turn, 2500 turns, 2900 turns etc..
Preferably, when the grapheme material is graphene oxide, step is carried out after step (2) or step (2 ')
(3)：Grapheme material combined mica dispersion liquid is subjected to reduction treatment and drying process；
Preferably, the mode of the reduction treatment includes any a kind in electronation, thermal reduction and microwave irradiation reduction
Or at least two kinds of combination.
When needing to carry out electronation, and deal with objects when be powder, it is necessary to which powder is disperseed to carry out in the solution.
When needing to be heat-treated or microwave reduction, and deal with objects, it is necessary to which liquid is dried into powder to enter when being liquid
OK.
Preferably, the process of the electronation is：Electronation is added into grapheme material combined mica dispersion liquid
Agent, reduction reaction is carried out, graphene combined mica powder is obtained after drying.
Preferably, the addition of the chemical reducing agent is more than 5 times of grapheme material, for example, 5.5 times, 6 times, 6.5
Again, it is 7. times, 7.5 times, 8. times, 8.5 times, 9. times, 9.5 times, 10. times, 10.5 times, 11 times, 11.5 times, 12 times, 12.5 times etc., excellent
Select more than 8 times, further preferred 10 times.
The addition of the chemical reducing agent is calculated with grapheme material, such as graphene oxide combined mica powder
Total amount be 101g, wherein there is graphene oxide 1g, then the addition of chemical reducing agent is more than 5g.
Chemical reducing agent provided by the invention is added into grapheme material combined mica dispersion liquid, although it is only used
Graphene oxide is restored to graphene, but its addition should compared to the reaction ratio of chemical reducing agent and pure graphene
When big more than 4 times, if addition of the chemical reducing agent into grapheme material combined mica dispersion liquid is very few, graphite can be caused
The reduction of alkene material is incomplete.
Preferably, the temperature of the reduction reaction is room temperature~95 DEG C, for example, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 55 DEG C, 60
DEG C, 75 DEG C, 80 DEG C, 85 DEG C etc., the time is 0.5~2h, such as 1h, 1.5h etc..
Preferably, the process of the thermal reduction is：After grapheme material combined mica dispersion liquid is dried into processing, enter
Row thermal reduction is handled, and obtains graphene combined mica powder.
Preferably, it is described thermal reduction processing temperature be 600~1000 DEG C, such as 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C,
850 DEG C, 900 DEG C, 950 DEG C etc., such as the time is 0.5~2h, such as 1h, 1.5h etc..
Preferably, the process of the microwave reduction is：After grapheme material combined mica dispersion liquid is dried into processing,
Microwave reduction processing is carried out, obtains graphene combined mica powder.
Preferably, the power of microwave reduction processing is 100~3000kW, for example, 150kW, 200kW, 350kW,
400kW、550kW、600kW、750kW、800kW、1050kW、1200kW、1400kW、1600kW、1800kW、2000kW、
2200kW, 2500kW, 2800kW etc., time are 5s~10min, such as 10s, 30s, 50s, 1min, 3min, 5min, 8min etc..
Preferably, the reduction treatment is to carry out microwave reduction processing again after electronation combines thermal reduction, is preferably：To
Chemical reducing agent is added in grapheme material combined mica dispersion liquid, carries out reduction reaction, after drying, carries out thermal reduction processing,
Microwave reduction processing is then carried out, obtains graphene combined mica powder.
Preferably, reducing agent used in the chemical reduction procedure includes L-AA, hydrazine hydrate, sodium citrate, company two
At least one kind of or at least two kinds of combination in sodium sulfite, hydroiodic acid, sodium metaphosphate, thiourea dioxide, metal-powder.
Preferably, the metal-powder includes zinc powder.
The combination of the reducing agent includes the combination of L-AA and hydrazine hydrate, sodium citrate and sodium dithionite
Combination, combination of sodium metaphosphate and sodium dithionite etc..
Preferably, the thermal reduction treatment conditions are to be warming up to 600~1000 DEG C under protective atmosphere, such as 650 DEG C,
700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C etc., 800 DEG C are preferably warming up under protective atmosphere.
Preferably, the thermal reduction processing time is more than 0.5h, such as 0.6h, 0.9h, 2.2h, 2.6h, 2.8h etc. is excellent
Select 0.5~2h；
Preferably, the protective atmosphere includes inert atmosphere or reducing atmosphere, preferably includes helium atmosphere, argon gas gas
Any a kind or at least two kinds of of combination in atmosphere, hydrogen atmosphere.
Preferably, the condition of the microwave reduction processing is microwave irradiation power density >=1000W/m3, such as 1000W/
m3、1200W/m3、1500W/m3、1800W/m3、2000W/m3Deng, 2~10s of irradiation, such as 3s, 4s, 5s, 6s, 7s, 8s etc..
Preferably, the drying includes spray drying.
As optimal technical scheme, the preparation method of grapheme material combined mica of the present invention comprises the following steps：
(1) mica is dipped in the mixed solution of the concentrated sulfuric acid and hydrogen peroxide and pre-processed；
(2) mica that step (1) pre-processes is mixed with graphene oxide dispersion, is modified processing, is aoxidized
Graphene combined mica suspension；
The graphene oxide combined mica dispersion liquid that (2 ') obtain step (2) is filtered, dried, and is obtained graphene oxide and is answered
Close mica；
(3) the graphene oxide combined mica that step (2 ') obtains is scattered in solution, obtains twice dispersing liquid, Xiang Qi
Middle addition chemical reducing agent is reduced, and after spray drying, is carried out thermal reduction processing, is handled by microwave reduction, obtain graphite
Alkene combined mica；
Preferably, the solvent of step (3) the twice dispersing liquid is hydrophilic solution, preferably includes water, can appoint with water
Any a kind or at least two kinds of of combination in the organic solvent of meaning ratio mixing.
The two of the object of the invention are to provide a kind of grapheme material combined mica, and the grapheme material combined mica passes through
The method of grapheme material combined mica described in the first purpose is prepared.
In grapheme material combined mica provided by the invention, graphene can exist in the form of Graphene derivative
Can be to exist in the form of the graphene for not containing non-carbon element.When the grapheme material is conductive, can assign
The good electric conductivity of the grapheme material combined mica, as graphene combined mica has excellent electric conductivity.
When needing to prepare graphene combined mica, and when the grapheme material added is oxidisability graphene, answered
Reduction treatment is carried out after closing powder, the combined mica after being reduced.
Preferably, in the grapheme material combined mica, the content of grapheme material is 1~20wt%, such as
2wt%, 4wt%, 5wt%, 7wt%, 8wt%, 9wt%, 12wt%, 14wt%, 15wt%, 17wt%, 18wt%, 19wt%
Deng.
The three of the object of the invention are to provide a kind of purposes of the grapheme material combined mica as described in the second purpose, described
Grapheme material combined mica is used as conductive material.
Compared with prior art, the invention has the advantages that：
(1) preparation method of the grapheme material combined mica provided in the present invention can be by grapheme material and mica jail
Consolidation is closed, and grapheme material can be made to be adsorbed among the sheet surfaces or lamella of mica, realizes the uniform of grapheme material
The scattered and strong bonded with inorganic material；
(2) preparation method of the grapheme material combined mica provided in the present invention, condition is easily-controllable, easy to operate, technique
Time is short, high to the modification efficiency of mica；
(3) in optimal technical scheme, graphene combined mica has excellent electric conductivity, and production prepared by different batches
The fluctuation of product electric conductivity is less than 1 ‰, in the graphene combined mica, graphene and mica strong bonded, and the materials'use life-span
It is long；
(4) preparation method of the grapheme material combined mica provided in the present invention (is such as divided for the performance of mica in itself
Dissipate property etc.) without generation deterioration；
(5) in graphene combined mica provided by the invention, on the premise of identical graphene is added (and combined mica
Graphene content it is identical), higher electric conductivity can be obtained.
Embodiment
Technical scheme is further illustrated below by embodiment.
Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair
Bright concrete restriction.
Embodiment 1
A kind of method for preparing grapheme material combined mica piece, comprises the following steps：
(1) weigh the mica powder of 20 μm of particle diameter, by washing, dry after, weigh 100g be dipped to 98% concentrated sulfuric acid and
Mixed solution (the volume ratio 4 of 30v% hydrogen peroxide:1) in, 10~120min of pretreatment is carried out at 100 DEG C, after obtaining pretreatment
Mica powder；
(2) step (1) pretreated mica powder is added and mica suspension is stirred into deionized water；
Add graphene oxide into deionized water, ultrasonic disperse is into graphene oxide dispersion under 1000~3000kW
(concentration 5mg/g)；
Mica suspension is mixed with graphene oxide dispersion, and 2.5h is stirred under 2500 turns of rotating speed, obtains oxygen
Graphite alkene combined mica dispersion liquid, the wherein mass ratio of graphene oxide and mica are 1:100；Aoxidized after drying
Graphene combined mica (graphene oxide content is 1wt%).
Embodiment 2
Step (3) is carried out after the step of embodiment 1 (2)：
Graphene oxide combined mica is dispersed again in the aqueous solution, according to graphene oxide and ascorbic acid 1:5
Addition adds 5g ascorbic acid and carries out electronation, then dries the solution after electronation and removes solvent, then will be dry
Powder after dry is placed in argon gas atmosphere, is heated to 800 DEG C, is heat-treated, and the powder after thermal reduction is put under an argon atmosphere
Microwave reduction processing (microwave power 800kW, time 10s) is carried out in microwave environment, obtains graphene combined mica powder (graphite
1%) alkene content is.
Embodiment 3~4
Difference with embodiment 2 is that the addition of ascorbic acid is according to graphene oxide and ascorbic acid in step (3)
1:10 addition (embodiment 3) and graphene oxide and ascorbic acid 1:2 addition (embodiment 4).
Embodiment 5~10
Difference with embodiment 2 is that mica suspension is different from graphene oxide dispersion mixed proportion, passes through adjustment
Both ratios, it is 2wt% (embodiment 5), 3wt% (embodiment 6), 5wt% (embodiment 7), 10wt% to obtain graphene content
(embodiment 8), 20wt% (embodiment 9), 22wt% (embodiment 10) graphene combined mica powder.
Embodiment 11~14
With differing only in for embodiment 2, in step (1) concentrated sulfuric acid and dioxygen water mixed liquid, both volume ratios are 2:1
(embodiment 11), 5:1 (embodiment 12), 1.8:1 (embodiment 13), 5.3:1 (embodiment 14).
Embodiment 15~16
With differing only in for embodiment 2, step (1) pretreatment temperature is 70 DEG C (embodiments 15) and 110 DEG C of (embodiments
16)。
Embodiment 17~18
With differing only in for embodiment 2, step (3) microwave power is 100kW (embodiment 17) and 3000kW (embodiments
18)。
Embodiment 19
With differing only in for embodiment 2, step (3) is that graphene oxide combined mica is dispersed again in into the aqueous solution
In, according to graphene oxide and ascorbic acid 1:5 addition adds 5g ascorbic acid and carries out electronation, then by chemistry also
Solution after original, which is dried, removes solvent, and then dried powder is placed in argon gas atmosphere, is heated to 800 DEG C, carries out heat also
Original, obtain graphene combined mica powder (graphene content is 1wt%).
Embodiment 20
With differing only in for embodiment 2, step (3) is done for graphene oxide combined mica is dispersed again in into the aqueous solution
Dried powder, is then placed in argon gas atmosphere by dry removing solvent, is heated to 800 DEG C, is heat-treated, after thermal reduction
Powder is placed in microwave environment under an argon atmosphere carries out microwave reduction processing (microwave power 800kW, time 10s), obtains stone
Black alkene combined mica powder (graphene content is 1wt%).
Embodiment 21~22
Difference with embodiment 2 is, the particle diameter of mica is 2 μm (embodiments 21), 2mm (embodiment 22), 2.5mm are (real
Apply example 23).
Comparative example 1
A kind of method for preparing graphene combined mica piece, comprises the following steps：
20 μm of mica powder of 100g particle diameters is added mica suspension is stirred into deionized water；
Add graphene oxide into deionized water, 1000~3000kW ultrasonic disperses are into graphene oxide dispersion
(concentration 5mg/g)；
Mica suspension is mixed with graphene oxide dispersion, and 2.5h is stirred under 2500 turns of rotating speed, obtains oxygen
Graphite alkene combined mica dispersion liquid, the wherein mass ratio of graphene oxide and mica are 1:100；Aoxidized after drying
Graphene combined mica (graphene oxide content is 1wt%).
Graphene oxide combined mica is dispersed again in the aqueous solution, according to graphene oxide and ascorbic acid 1:5
Addition adds 5g ascorbic acid and carries out electronation, then dries the solution after electronation and removes solvent, then will be dry
Powder after dry is placed in argon gas atmosphere, is heated to 800 DEG C, is heat-treated, and the powder after thermal reduction is put under an argon atmosphere
Microwave reduction processing (microwave power 800kW, time 10s) is carried out in microwave environment, obtains graphene combined mica powder (graphite
1%) alkene content is.
Performance test：
(1) resistivity measurement of grapheme material combined mica：
The method of testing of the resistivity measurement utilizes resistivity measurement according to method of testing described in HG/T 4764-2014
Device measures the resistivity of above-mentioned material.
(2) grapheme material combined mica firmness is tested：
Grapheme material combined mica is added to the water scattered, filtered afterwards, and repeat to disperse-filtration step 50
It is secondary, test washing resistivity；
Above-described embodiment and test case are collected tabulated below：
The performance test results of the embodiment 2~22 of table 1 and comparative example 1
The method of the invention is can be seen that by the surface treatment to mica powder via above-described embodiment and comparative example,
Acquisition can be in the graphene conductive mica that mica surface closely coats.Chemical reducing agent is can be seen that from embodiment 2,3,4
2 times of addition graphene oxide combined mica (embodiment 4) compares more than 5 times of addition, and resistivity, which has, to be decreased obviously, and is pushed away
Survey is probably because although the requirement that the addition of reducing agent reduces apparently higher than graphene oxide, is not enough to and aoxidizes
The graphene oxide disperseed in graphene combined mica fully contacts, therefore causes to reduce insufficient, and resistivity is slightly higher.From implementation
Example 1,5~10 is as can be seen that as the amount of graphene compound in graphene combined mica is more and more, and its resistivity is increasingly
It is low, by experiment it can be found that when in graphene oxide combined mica the mass ratio of graphene oxide and mica 0.5~50:
Between 100, when fully being reduced, resistivity can be understood as electronation in 0.8~330 Ω cm, so-called fully reduction
With reference to microwave reduction processing is carried out after thermal reduction again.It is from embodiment 1,11~14 as can be seen that dense in the pretreatment process of mica
The volume ratio of sulfuric acid and hydrogen peroxide is 2~5:1 condition, it can assign graphene combined mica better electric conductivity, push away
Survey be probably because the Pretreatment more effectively can be opened mica splittings, or by mica splittings surface or between
With reference to reactive species, key good with subsequent oxidation graphene and, graphene is preferably combined with mica, improve electric conductivity.
Carrying out microwave reduction processing again after can be seen that electronation combination thermal reduction from the result of embodiment 1,19,20 can be abundant
Graphene oxide is reduced, obtains more preferable electrical conductivity, but good electricity can also be obtained by only carrying out 2 therein or 1
Conductance effect.
Embodiment 23
Amino graphene, specific steps are substituted for the quality such as step (2) described graphene oxide that are distinguished as of embodiment 1
For：
(1) weigh the mica powder of 20 μm of particle diameter, by washing, dry after, weigh 100g be dipped to 98% concentrated sulfuric acid and
Mixed solution (the volume ratio 4 of 30v% hydrogen peroxide:1) in, 10~120min of pretreatment is carried out at 100 DEG C, after obtaining pretreatment
Mica powder；
(2) step (1) pretreated mica powder is added and mica suspension is stirred into deionized water；
Amino graphene is added to deionized water and ethanol (volume ratio 1:1) in mixed liquor, under 1000~3000kW
Ultrasonic disperse ammonification base graphene dispersing solution (concentration 5mg/g)；
Mica suspension is mixed with amino graphene dispersing solution, and 2.5h is stirred under 2500 turns of rotating speed, obtains ammonia
Base graphene combined mica dispersion liquid, the wherein mass ratio of amino graphene and mica are 1:100；Amino is obtained after drying
Graphene combined mica (amino graphene content is 1wt%).
Method of testing test electricity described in amino graphene combined mica HG/T 4764-2014 prepared by embodiment 23
Resistance rate is 330 Ω cm.
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (9)
- A kind of 1. method of grapheme material combined mica, it is characterised in that methods described comprises the following steps：(1) mica is dipped in oxidizing solution and pre-processed；(2) mica that step (1) pre-processes is mixed with grapheme material dispersion liquid, is modified processing, obtains graphene material Expect combined mica dispersion liquid；Alternatively, the grapheme material combined mica dispersion liquid mistake that step (2 ') obtains step (2) is carried out after step (2) Filter, dry, obtain grapheme material combined mica.
- 2. the method as described in claim 1, it is characterised in that the oxidizing solution is molten for the mixing of the concentrated sulfuric acid and hydrogen peroxide Liquid；Preferably, in the oxidizing solution, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 2~5:1, preferably 7~9:3, wherein double Oxygen water concentration is based on 30v%；Preferably, the temperature of the pretreatment is 70~110 DEG C, preferably 80~90 DEG C；Preferably, the time of the pretreatment is 10~120min, preferably 40~70min.
- 3. method as claimed in claim 1 or 2, it is characterised in that the grapheme material includes having graphene sheet layer knot Appointing in the material of structure, including single-layer graphene, bilayer graphene, multi-layer graphene, graphene oxide and Graphene derivative The combination of a kind or at least two kinds of of meaning, preferably graphene oxide and/or Graphene derivative, further preferred graphene oxide；Preferably, the particle diameter of the mica is 2 μm~2mm；Preferably, the dispersant of the grapheme material dispersion liquid is hydrophilic solution, preferably includes water, can arbitrarily compare with water Any a kind or at least two kinds of of combination in the organic solvent of example mixing.
- 4. the method as described in one of claims 1 to 3, it is characterised in that the mixed proportion of the grapheme material and mica For 0.5~50:100, preferably 1~20:100；Preferably, during the modification, it is stirred and is ultrasonically treated；Preferably, the ultrasonic power is 1000~3000kW；Preferably, the stir speed (S.S.) is 800~3000 turns.
- 5. the method as described in one of Claims 1 to 4, it is characterised in that when the grapheme material is graphene oxide, Step (3) is carried out after step (2) or step (2 ')：Grapheme material combined mica dispersion liquid is subjected to reduction treatment and drying Processing；Preferably, the mode of the reduction treatment include electronation, thermal reduction and microwave irradiation reduction in any a kind or extremely Few 2 kinds combination；Preferably, the process of the electronation is：Chemical reducing agent is added into grapheme material combined mica dispersion liquid, is entered Row reduction reaction, graphene combined mica powder is obtained after drying；Preferably, the addition of the chemical reducing agent is more than 5 times of grapheme material, preferably more than 8 times, further preferably 10 times；Preferably, the temperature of the reduction reaction is room temperature~95 DEG C, and the time is 0.5~2h；Preferably, the process of the thermal reduction is：After grapheme material combined mica dispersion liquid is dried into processing, heat is carried out Reduction treatment, obtain graphene combined mica powder；Preferably, the temperature of the thermal reduction processing is 600~1000 DEG C, and the time is 0.5~2h；Preferably, the process of the microwave reduction is：After grapheme material combined mica dispersion liquid is dried into processing, carry out Microwave reduction processing, obtains graphene combined mica powder；Preferably, the power of the microwave reduction processing is 100~3000kW, and the time is 5s~10min；Preferably, the reduction treatment is to carry out microwave reduction processing again after electronation combines thermal reduction, is preferably：To graphite Chemical reducing agent is added in alkene Material cladding mica dispersion liquid, carries out reduction reaction, after drying, carries out thermal reduction processing, then Microwave reduction processing is carried out, obtains graphene combined mica powder.
- 6. method as claimed in claim 5, it is characterised in that reducing agent used includes L-AA, hydrazine hydrate, citric acid At least one kind of or at least two kinds of group in sodium, sodium dithionite, hydroiodic acid, sodium metaphosphate, thiourea dioxide, metal-powder Close；Preferably, the metal-powder includes zinc powder；Preferably, the thermal reduction treatment conditions are to be warming up to 600~1000 DEG C, preferably under protective atmosphere under protective atmosphere It is warming up to 800 DEG C；Preferably, the thermal reduction processing time is more than 0.5h, preferably 0.5~2h；Preferably, the protective atmosphere includes inert atmosphere or reducing atmosphere, preferably include helium atmosphere, argon gas atmosphere, Any a kind or at least two kinds of of combination in hydrogen atmosphere；Preferably, the condition of the microwave reduction processing is microwave irradiation power density >=1000W/m3, irradiate 2~10s；Preferably, the drying includes spray drying.
- 7. the method as described in one of claim 1~6, it is characterised in that comprise the following steps：(1) mica is dipped in the mixed solution of the concentrated sulfuric acid and hydrogen peroxide and pre-processed；(2) mica that step (1) pre-processes is mixed with graphene oxide dispersion, is modified processing, obtains graphite oxide Alkene combined mica suspension；The graphene oxide combined mica dispersion liquid that (2 ') obtain step (2) is filtered, dried, and obtains the compound cloud of graphene oxide It is female；(3) the graphene oxide combined mica that step (2 ') obtains is scattered in solution, obtains twice dispersing liquid, added thereto Enter chemical reducing agent to be reduced, after spray drying, carry out thermal reduction processing, then handled by microwave reduction, obtain graphite Alkene combined mica；Preferably, the solvent of step (3) the twice dispersing liquid is hydrophilic solution, preferably includes water, can arbitrarily compare with water Any a kind or at least two kinds of of combination in the organic solvent of example mixing.
- A kind of 8. grapheme material combined mica, it is characterised in that the grapheme material combined mica by claim 1~ The method of grapheme material combined mica described in one of 7 is prepared；Preferably, in the grapheme material combined mica, the content of grapheme material is 1~20wt%.
- A kind of 9. purposes of grapheme material combined mica as claimed in claim 8, it is characterised in that the grapheme material Combined mica is used as conductive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711059856.6A CN107814390A (en) | 2017-11-01 | 2017-11-01 | A kind of grapheme material combined mica, preparation method and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711059856.6A CN107814390A (en) | 2017-11-01 | 2017-11-01 | A kind of grapheme material combined mica, preparation method and purposes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107814390A true CN107814390A (en) | 2018-03-20 |
Family
ID=61603624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711059856.6A Pending CN107814390A (en) | 2017-11-01 | 2017-11-01 | A kind of grapheme material combined mica, preparation method and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107814390A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993603A (en) * | 2018-08-01 | 2018-12-14 | 江阴双良石墨烯光催化技术有限公司 | A method of adhering to graphene photo-catalyst in stone surface |
| CN109092281A (en) * | 2018-08-01 | 2018-12-28 | 江阴双良石墨烯光催化技术有限公司 | A method of adhering to graphene photo-catalyst on artificial aquatic weed surface |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112299A (en) * | 2008-08-08 | 2011-06-29 | 埃克森美孚化学专利公司 | Graphite nanocomposites |
| CN102390841A (en) * | 2011-07-27 | 2012-03-28 | 哈尔滨工业大学 | Preparation method of loose sericite powder |
| CN103183353A (en) * | 2011-12-29 | 2013-07-03 | 中国科学院成都有机化学有限公司 | Conductive mica powder and preparation method thereof |
| CN104030280A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Preparation method of graphene paper |
| CN105670344A (en) * | 2016-02-06 | 2016-06-15 | 浙江顺虎德邦涂料有限公司 | Preparation method of cuprous oxide/mica composite packing having antiseptic and antifouling functions |
-
2017
- 2017-11-01 CN CN201711059856.6A patent/CN107814390A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112299A (en) * | 2008-08-08 | 2011-06-29 | 埃克森美孚化学专利公司 | Graphite nanocomposites |
| CN102390841A (en) * | 2011-07-27 | 2012-03-28 | 哈尔滨工业大学 | Preparation method of loose sericite powder |
| CN103183353A (en) * | 2011-12-29 | 2013-07-03 | 中国科学院成都有机化学有限公司 | Conductive mica powder and preparation method thereof |
| CN104030280A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Preparation method of graphene paper |
| CN105670344A (en) * | 2016-02-06 | 2016-06-15 | 浙江顺虎德邦涂料有限公司 | Preparation method of cuprous oxide/mica composite packing having antiseptic and antifouling functions |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993603A (en) * | 2018-08-01 | 2018-12-14 | 江阴双良石墨烯光催化技术有限公司 | A method of adhering to graphene photo-catalyst in stone surface |
| CN109092281A (en) * | 2018-08-01 | 2018-12-28 | 江阴双良石墨烯光催化技术有限公司 | A method of adhering to graphene photo-catalyst on artificial aquatic weed surface |
| CN108993603B (en) * | 2018-08-01 | 2021-04-13 | 江苏双良环境科技有限公司 | Method for attaching graphene photocatalyst to surface of stone |
| CN109092281B (en) * | 2018-08-01 | 2021-04-13 | 江苏双良环境科技有限公司 | Method for attaching graphene photocatalyst to surface of artificial waterweed |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jakhar et al. | Microwave reduction of graphene oxide | |
| Calpa et al. | Preparation of sulfide solid electrolytes in the Li 2 S–P 2 S 5 system by a liquid phase process | |
| CN104538670B (en) | A kind of full solid state polymer electrolyte, its preparation method and application | |
| CN105798320B (en) | A kind of method of low temperature preparation copper nanoparticle | |
| CN108134090A (en) | A kind of nanometer of bismuth/carbon composite and preparation method thereof | |
| CN104289722B (en) | A kind of preparation method of nanometer silver | |
| KR101745547B1 (en) | Manufacturing method of carbon-metal nano composites by self-heating and graphene-metal nano composite manufactured by the same | |
| CN109888256B (en) | Si @ SiOx@ nitrogen doped TiO2-δMaterial, preparation method and application thereof | |
| CN106670501A (en) | Preparing method for graphene-metal base composite powder | |
| CN106216705A (en) | A kind of preparation method of 3D printing fine grained simple substance globular metallic powder | |
| CN107628628A (en) | A kind of graphene modified inorganic material, preparation method and purposes | |
| CN107814390A (en) | A kind of grapheme material combined mica, preparation method and purposes | |
| CN106410199A (en) | Preparation method of graphene/ferro-tin alloy composite anode material for lithium ion battery | |
| CN102502610A (en) | Simple method for preparing a large amount of graphene | |
| CN104259472B (en) | A kind of organic composite of superfine sheet copper powder and preparation method thereof | |
| CN111496266A (en) | Environment-friendly conductive nano copper ink and preparation method thereof | |
| CN106847364A (en) | A kind of preparation method and application of the laminated film of copper-zinc-tin-sulfur and three-dimensional grapheme | |
| CN105315964B (en) | A kind of synthetic method of ferroso-ferric oxide conducting polymer graphene tri compound wave absorbing agent | |
| CN105858648B (en) | A kind of preparation method of graphene | |
| Tan et al. | Solid-state microwave synthesis CuO/CNT: a high-performance electrode material for supercapacitors | |
| CN102586800B (en) | Preparation method of nano-copper powder | |
| CN108134092A (en) | A kind of nanometer of lead/carbon composite and preparation method thereof | |
| CN114267833A (en) | Method for coating ternary cathode material with sulfide solid electrolyte | |
| CN113540430A (en) | Preparation method and application of graphene-based composite electrode material | |
| CN109179387B (en) | Method for preparing graphene and graphene prepared by method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180320 |
|
| RJ01 | Rejection of invention patent application after publication |