CN106830084B - The preparation method of two-dimensional material powder and its dispersion liquid - Google Patents
The preparation method of two-dimensional material powder and its dispersion liquid Download PDFInfo
- Publication number
- CN106830084B CN106830084B CN201710037954.3A CN201710037954A CN106830084B CN 106830084 B CN106830084 B CN 106830084B CN 201710037954 A CN201710037954 A CN 201710037954A CN 106830084 B CN106830084 B CN 106830084B
- Authority
- CN
- China
- Prior art keywords
- dimensional material
- preparation
- dispersion
- ball milling
- combination
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0648—After-treatment, e.g. grinding, purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
Abstract
The present invention provides the preparation methods of two-dimensional material powder and its dispersion liquid, the described method comprises the following steps: two-dimensional material raw material being carried out ball milling, obtains solid material；Just dispersion solvent is added into obtained solid material, carries out just ultrasonic treatment, obtains dispersion liquid of the two-dimensional material in first dispersion solvent；Precipitating reagent is added in the dispersion liquid in first dispersion solvent to the two-dimensional material, is centrifuged and dries after precipitating is complete, obtain two-dimensional material powder.Two-dimensional material powder dispersion the preparation method comprises the following steps: by two-dimensional material powder be added redisperse agent in, be then sonicated, obtain dispersion liquid of the two-dimensional material in redisperse agent.Compared with the conventional method, this method has many advantages, such as from a wealth of sources, and easy to operate, prepared two-dimensional material powder sample can obtain fine dispersion in multi-solvents, the concentration of its dispersion liquid is higher, and the practical application and large-scale production for two-dimensional material have important application value.
Description
Technical field
The invention belongs to technical field of inorganic nano-material preparation, are related to the preparation side of two-dimensional material powder and its dispersion liquid
Method.
Background technique
Using graphene as the two-dimensional material of representative, due to its with characteristics such as light outstanding, electricity, sensing and energy stores and
It is concerned.In recent years, studying more two-dimensional material is mainly graphene and class grapheme two-dimension material.Wherein, more allusion quotation
The class grapheme two-dimension material of type has two chalcogenide of transition metal, such as MoS2And WS2Deng by IVB, VB in the periodic table of elements,
The layer structure of the sulfur families nonmetalloid such as the transition metal of VIB, VIIB and VIII group element and S, Se and Te composition.In addition,
Class grapheme two-dimension material also includes BN (h-BN) of hexagonal structure etc..
So far, the powder two-dimensional material for the two-dimensional material registered in document and patent has many special properties,
The more and more research interests of people are caused, how to have realized that the scale of single layer or few layer two-dimensional material prepares nature and just becomes
Current research hotspot.At this stage, the preparation of two-dimensional material still remains the following problem: firstly, prepare with scale is two-dimentional
Material often destroys its intrinsic structure；Secondly, using a large amount of solvent during preparing two-dimensional material, while also needing
Additional that such as surfactant is added to promote the removing of two-dimensional material, final product is often with the shape of two-dimensional material dispersion liquid
Formula exists.On the one hand the presence of a large amount of solvents can increase considerably cost of wheeling and risk safety in industrialization engineering, another
The use of aspect single solvent is difficult to meet the requirement of different field.And the use of the additives such as surfactant can make to prepare work
Skill is complicated, can largely effect on its performance a small amount of residual.Therefore, the preparation of two-dimensional material powder and its dispersion liquid is developed
Method has great theory and realistic meaning.
The main policies of two-dimensional material prepare with scale are cut in specific solvent by ultrasound, at a high speed by two-dimensional material
It cuts or the additional physical mechanical effect removings such as ball milling is prepared, from the angle of its dispersion solvent, can be classified as organic
Polar solvent and water two major classes.Wherein, organic polar solvent is primarily referred to as selection and close organic of two-dimensional material surface tension
Solvent, such as NMP and DMF.J.N.Coleman et al. has studied a kind of method using ultrasonic disperse and centrifuge separation, obtains
MoS2、WS2And MoSe2Etc. two-dimensional materials NMP dispersion liquid (Two-dimensional nanosheets produced by
liquid exfoliation oflayered materials.J.N.Coleman,et al.Science,2011,331:
568-571.).Y.Hernandez et al. selects flaky graphite for raw material, by ultrasonic disperse and centrifuge separation, obtains stone
NMP dispersion liquid (the High-yield production of graphene by liquid-phase exfoliation of black alkene
of graphite.Y.Hernandez,et al.Nature Nanotechnology,Vol.3,No.9,563–568,
2008.).Such methods can the very effective intrinsic two-dimensional material for obtaining 1~10 layer of few layer structure, but high boiling solvent
Use, limit further applying for two-dimensional material；Meanwhile using for a large amount of organic solvents to turn in course of industrialization
Fortune cost and risk all greatly promote.CN 104495828A discloses a kind of method that liquid phase stripping method prepares graphene, benefit
Graphite is obtained by ultrasonic disperse with surfactants such as sodium taurocholate, lauryl sodium sulfate and neopelexes
The aqueous dispersions of alkene.CN 103910354A discloses a kind of method that scale water phase prepares graphene, utilizes and contains hydrogen-oxygen
The alkaline aqueous solution for changing sodium, potassium hydroxide, lithium hydroxide and sodium carbonate etc. is finally obtained graphene by ultrasonic disperse
Aqueous dispersions.Dispersing agent such as surfactant uses so that need additionally to add cleaning step in preparation process, while residual
The dispersing agent stayed may have a huge impact the quality of final two-dimensional material.If not selecting surfactant, need
Two-dimensional material is pre-processed, by taking graphene as an example, CN 103935995A discloses a kind of stable graphene colloid dispersion solution
Preparation method first passes through improved Hummer ' s method and prepares graphene oxide, and further reduction is to obtain graphene.But
This method obtains redox graphene colloidal dispersion, and quality can not compare favourably with graphene.
After preparing two-dimensional material dispersion liquid, the usual way of powder is obtained for vacuum filtration and drying, only on a small quantity specially
Powder after benefit report is dry can disperse back again in organic solvent.CN 103723708A, which discloses a kind of single-layer graphene, to be had
Machine solution manufacturing method, the method obtain graphene dispersing solution by ultrasonic disperse in organic solvent, then pass through pumping
Filter, washing and drying, can get graphene solid powder.This amount of powder can be dispersed again in organic solvent by ultrasound
In.CN 104556020A discloses a kind of preparation method of graphene alcohol dispersion liquid, and graphite is first added to N- methyl pyrrole
Ultrasonic removing is carried out in pyrrolidone and centrifuge separation obtains the dispersion liquid of graphene, passes through the graphene powder after filtering and drying
It can be re-dispersed into ethyl alcohol, repeat filtering and redisperse, the alcohol dispersion liquid of graphene may finally be obtained.Although above-mentioned side
Method is more effective, but still remains some problems.It is less than the two-dimensional material of filter membrane firstly, for size, such as two-dimensional material amount
Son point and quantum piece etc., suction filtration can not play the role of effective；Secondly, suction filtration process duration is longer, greatly limit
Large-scale production is made；Finally, the powder after dry whether can effectively be dispersed to again in multi-solvents always be it is outstanding and
Pending problem.
Body and its multi-solvent disperse liquid and preparation method thereof, there is following common problem: such as complex process, higher cost and consumption
When it is longer etc., and be unable to satisfy the demand of large-scale production.That just there is an urgent need to Devoting Major Efforts To Developings is simple, efficient and inexpensive for this
Universal method is used to prepare two-dimensional material powder and its dispersion liquid, and the breakthrough in preparation method will certainly greatly accelerate it
Process of industrialization.
Summary of the invention
For complex process existing in the prior art, higher cost is taken a long time, and two-dimensional material powder and its not
The problem of with the poor universality in solvent dispersions and being difficult to realize large-scale production, the present invention provides two-dimensional material powder and
The preparation method of its dispersion liquid.The method of the invention has many advantages, such as two-dimensional material from a wealth of sources, easy to operate, prepared
Powder sample all has good dispersion performance in multi-solvents, and the concentration of dispersion liquid is higher, for the reality of two-dimensional material
Border application and large-scale production have important application value.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the described method comprises the following steps the present invention provides two-dimensional material raw powder's production technology:
(1) two-dimensional material raw material is subjected to ball milling, obtains solid material；
(2) just dispersion solvent is added in obtained solid material in step (1), carries out just ultrasonic treatment, obtains two-dimentional material
Expect the dispersion liquid in first dispersion solvent；
(3) precipitating reagent is added in the dispersion liquid in first dispersion solvent to two-dimensional material described in step (2), precipitating is complete
After be centrifuged or filter, obtain two-dimensional material powder after dry.
In the present invention, by two-dimensional material carry out just be ultrasonically treated purpose be the solid material that step (1) is obtained into
Row ultrasound removing.
In the present invention, the purpose that two-dimensional material carries out precipitation process is two-dimensional material powder is prepared by precipitating
Body overcomes the problems, such as that the two-dimensional material for being less than filter membrane for size present in existing filter method can not play and efficiently separates；
Meanwhile it is long to also overcome the duration in existing filter method, the problem of can not being mass produced.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, step (1) the two-dimensional material raw material is graphite, hexagonal boron nitride, two
Any one in molybdenum sulfide, tungsten disulfide, two selenizing molybdenums or two tungsten selenides or at least two combination, the combination is typical but non-
Limitative examples have: the combination of the combination of graphite and hexagonal boron nitride, molybdenum disulfide and tungsten disulfide, tungsten disulfide and two selenizings
The combination of molybdenum, the combination of two selenizing molybdenums and two tungsten selenides, the combination of graphite, hexagonal boron nitride and molybdenum disulfide, molybdenum disulfide, two
The combination of tungsten sulfide and two selenizing molybdenums, the combination of tungsten disulfide, two selenizing molybdenums and two tungsten selenides, graphite, hexagonal boron nitride, two sulphur
Change the combination of molybdenum and tungsten disulfide, the group of graphite, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, two selenizing molybdenums and two tungsten selenides
Close etc..
Preferably, the size of step (1) the two-dimensional material raw material be 0.1 μm~100 μm, such as 0.1 μm, 1 μm, 5 μm,
10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable, and preferably 0.5 μm~10 μm.
In the present invention, the size of the two-dimensional material raw material is statement customary in the art, belongs to clear statement.
As currently preferred technical solution, step (1) specific method that two-dimensional material raw material is carried out to ball milling
The following steps are included:
(a) two-dimensional material raw material and ball milling ball are mixed, carries out ball milling；
(b) it is dried in vacuo after separating the solid material after ball milling in step (a) with ball milling ball, obtains solids
Material；
Or,
(a ') mixes two-dimensional material raw material, grinding aid and ball milling ball, carries out ball milling；
After (b ') separates the solid material after ball milling in step (a ') with ball milling ball, it is added and washes into the material after separation
Solvent is washed, is washed, vacuum drying obtains solid material.
In the present invention, usually when preparing 1 μm or less two-dimensional material, needs to be added grinding aid as adjuvant and carry out ball
Mill.
As currently preferred technical solution, step (a) and the material of ball milling ball described in step (a ') are independent
For any one in agate, zirconium dioxide, stainless steel, modulation steel, hard tungsten carbide, silicon nitride or alundum or at least two
Combination, the combination is typical but non-limiting example has: the combination of agate and zirconium dioxide, the group of stainless steel and modulation steel
It closes, the combination of hard tungsten carbide and silicon nitride, the combination of silicon nitride and alundum, agate, zirconium dioxide, stainless steel and modulation
The combination of steel, stainless steel, the combination for modulating steel, hard tungsten carbide and silicon nitride, modulation steel, hard tungsten carbide, silicon nitride and burning
Tie the combination of corundum, agate, zirconium dioxide, stainless steel, modulation steel, hard tungsten carbide and the combination of silicon nitride etc..
Preferably, step (a) and the diameter of ball milling ball described in step (a ') they are independently 0.5mm~20mm, such as
0.5mm, 1mm, 3mm, 5mm, 7mm, 10mm, 13mm, 15mm, 17mm or 20mm etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.
Preferably, step (a) and the time of ball milling described in step (a ') they are independently 0.5h~120h, such as
0.5h, 1h, 5h, 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h, 110h or 120h etc., it is not limited to
Cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 1h~50h.
Preferably, step (a) and the additional amount of ball milling ball described in step (a ') are independently that the two-dimensional material is former
1 times~1000 times for expecting quality, such as 1 times, 10 times, 50 times, 100 times, 200 times, 300 times, 400 times, 500 times, 600 times, 700
Again, 800 times, 900 times or 1000 times etc., it is not limited to cited numerical value, other interior unlisted numbers of the numberical range
Be worth it is equally applicable, preferably 50 times~300 times.
Preferably, the additional amount of grinding aid described in step (a ') is 0 times~100 times of the two-dimensional material material quality
It and does not include 0 times, such as 1 times, 5 times, 10 times, 20 times, 30 times, 40 times, 50 times, 60 times, 70 times, 80 times, 90 times or 100 times
Deng, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 1 times~
30 times.
Preferably, grinding aid described in step (a ') is by anion and cation composition, wherein cation is IA race element
Cation, Group IIA element cation or ammonium root cation in any one or at least two combination, wherein IA race element
Cation be lithium ion, sodium ion, potassium ion, rubidium ion or cesium ion in any one or at least two combination, Group IIA
The cation of element is the combination of any one in beryllium ion, magnesium ion, calcium ion, strontium ion or barium ions or at least two；
Anion is hydroxide ion, chloride ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate anion, phosphoric acid
Any one in hydrogen radical ion, dihydrogen phosphate ions, carbanion, bicarbonate ion or citrate ion or at least
Two kinds of combination, the combination is typical but non-limiting example has: the combination of hydroxide ion and chloride ion, nitrate ion and
The group of the combination of the combination of sulfate ion, sulfate ion and hydrogen sulfate ion, phosphate anion and phosphoric acid hydrogen radical ion
Close, the combination of dihydrogen phosphate ions and carbanion, the combination of carbanion and bicarbonate ion, bicarbonate radical from
The combination of son and citrate ion, hydroxide ion, chloride ion, nitrate ion, sulfate ion and hydrogen sulfate ion
Combination, hydrogen sulfate ion, phosphate anion, phosphoric acid hydrogen radical ion, dihydrogen phosphate ions, carbanion, bicarbonate
Radical ion and the combination of citrate ion etc..
Preferably, cleaning solvent described in step (b ') is any one in water, hydrochloric acid, sulfuric acid or nitric acid or at least two
Combination, the combination is typical but non-limiting example is by the sulphur that the aqueous hydrochloric acid solution that hydrochloric acid and water forms, sulfuric acid and water form
The aqueous solution of the nitric acid of the aqueous solution of acid, nitric acid and water composition, the combination of hydrochloric acid and sulfuric acid, the combination of sulfuric acid and nitric acid, hydrochloric acid,
Sulfuric acid and the combination of nitric acid etc..
Preferably, it is washed described in step (b ') are as follows: clean the grinding aid in the solid material after the ball milling completely
Fall.
Preferably, vacuum drying temperature described in step (b) and (b ') is independently 0 DEG C~100 DEG C, such as 0 DEG C,
10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable, and preferably 20 DEG C~60 DEG C.
As currently preferred technical solution, just dispersion solvent is N-Methyl pyrrolidone, N- second described in step (2)
Vinyl pyrrolidone, N- cyclohexyl pyrrolidone, n-octylpyrrolidone, N-dodecylpyrrolidone, gamma-butyrolacton, first
Any one in amide, N-METHYLFORMAMIDE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide or extremely
Few two kinds of combination, the combination is typical but non-limiting example has: N-Methyl pyrrolidone and n-vinyl pyrrolidone
Combination, the combination of N- cyclohexyl pyrrolidone and n-octylpyrrolidone, the group of N-dodecylpyrrolidone and gamma-butyrolacton
It closes, the combination of formamide and N-METHYLFORMAMIDE, the combination of n,N-Dimethylformamide and n,N-dimethylacetamide, N, N- bis-
The combination of methylacetamide and dimethyl sulfoxide, N-Methyl pyrrolidone, n-vinyl pyrrolidone and N- cyclohexyl pyrrolidines
The combination of ketone, the combination of n-octylpyrrolidone, N-dodecylpyrrolidone, gamma-butyrolacton and formamide, formamide, N-
The combination of methylformamide, n,N-Dimethylformamide and n,N-dimethylacetamide, gamma-butyrolacton, formamide, N- methyl first
The combination of amide, n,N-Dimethylformamide, n,N-dimethylacetamide and dimethyl sulfoxide, N-Methyl pyrrolidone, N- second
Vinyl pyrrolidone, N- cyclohexyl pyrrolidone, n-octylpyrrolidone, N-dodecylpyrrolidone, gamma-butyrolacton and first
The combination etc. of amide.
Preferably, the Vltrasonic device in being just ultrasonically treated described in step (2) is probe type Vltrasonic device and/or water-bath type
Vltrasonic device.
Preferably, described in step (2) just be ultrasonically treated ultrasonic power be 50W~1000W, such as 50W, 100W,
200W, 300W, 400W, 500W, 600W, 700W, 800W, 900W or 1000W etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range, preferably 100W~500W.
Preferably, described in step (2) just be ultrasonically treated ultrasonic time be 0.5h~120h, such as 0.5h, 1h, 5h,
10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h, 110h or 120h etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 1h~50h.
Preferably, the concentration of two-dimensional material in the dispersion liquid in first dispersion solvent of two-dimensional material described in step (2) is
0.01mg/mL~100mg/mL, for example, 0.01mg/mL, 0.05mg/mL, 0.1mg/mL, 0.5mg/mL, 1mg/mL, 5mg/mL,
10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL or
100mg/mL etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably
For 0.1mg/mL~10mg/mL.
As currently preferred technical solution, precipitating reagent described in step (3) is methyl formate, Ethyl formate, formic acid
Propyl ester, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methanol, ethyl alcohol, isopropanol,
Any one in n-hexane, normal heptane, normal octane or petroleum ether or at least two combination, the combination is typical but non-limiting
Example has: the combination of the combination of methyl formate and Ethyl formate, propyl formate and methyl acetate, methyl acetate and ethyl acetate
Combination, the combination of propyl acetate and methyl propionate, the combination of methyl propionate and ethyl propionate, the group of methanol, ethyl alcohol and isopropanol
Close, the combination of isopropanol, n-hexane and normal heptane, the combination of normal heptane, normal octane and petroleum ether, methyl formate, Ethyl formate,
The combination of propyl formate, methyl acetate and ethyl acetate, the combination of methyl acetate, ethyl acetate, propyl acetate and methyl propionate,
The combination of ethyl propionate, propyl propionate, methanol, ethyl alcohol, isopropanol and n-hexane, ethyl alcohol, isopropanol, n-hexane, normal heptane, just
Octane and the combination of petroleum ether etc..
Preferably, the additional amount of precipitating reagent described in step (3) are as follows: the precipitating reagent disperses with the two-dimensional material just
The volume ratio of dispersion liquid in solvent be 1:(0.01~100), such as 1:0.01,1:1,1:5,1:10,1:20,1:30,1:40,
1:50,1:60,1:70,1:80,1:90 or 1:100 etc., it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable, preferably 1:(0.5~10).
Preferably, the revolving speed of centrifuge separation described in step (3) is 500r/min~10000r/min, such as 500r/
min、1000r/min、2000r/min、3000r/min、4000r/min、5000r/min、6000r/min、7000r/min、
8000r/min, 9000r/min or 10000r/min etc., it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable, preferably 1000r/min~6000r/min.
Preferably, the centrifugation time of centrifuge separation described in step (3) be 1min~120min, such as 1min, 10min,
20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min etc., but simultaneously
It is not limited only to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, preferably 5min~60min.
Preferably, the aperture of filter membrane or filter paper used is 1 μm~100 μm in filtering described in step (3), such as 1 μm, 5 μ
M, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm etc., it is not limited to cited
Numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, described in step (3) it is dry for vacuum drying, heating is dry or freeze-drying in any one or at least
Two kinds of combination, the combination is typical but non-limiting example has: the combination of vacuum drying and heating drying, heating are dry and cold
Dry combination is lyophilized, vacuum drying, heating are dried and frozen dry combination etc..
Second aspect, the present invention provides the preparation method of two-dimensional material powder dispersion, the methods are as follows:
The two-dimensional material powder that above-mentioned preparation method is prepared is added in redisperse agent, is then sonicated, is obtained
To dispersion liquid of the two-dimensional material in redisperse agent.
Two-dimensional material made from the method has preferable pervasive performance through the invention, can be scattered in again a variety of molten
In agent, and still maintain preferable performance.
As currently preferred technical solution, the redisperse solvent is water, methanol, ethyl alcohol, isopropanol, acetone, fourth
Ketone, N-Methyl pyrrolidone, n-vinyl pyrrolidone, N- cyclohexyl pyrrolidone, n-octylpyrrolidone, N- dodecyl
Pyrrolidones, gamma-butyrolacton, formamide, N-METHYLFORMAMIDE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, diformazan
Any one in base sulfoxide, benzene, chlorobenzene, bromobenzene, benzonitrile, benzaldehyde, Ergol or benzyl ether or at least two group
It closes, the combination is typical but non-limiting example has: the combination of water and methanol, the combination of ethyl alcohol, isopropanol and acetone, butanone,
The combination of N-Methyl pyrrolidone and n-vinyl pyrrolidone, n-vinyl pyrrolidone, N- cyclohexyl pyrrolidone and N-
The combination of octylpyrrolidone, the combination of N-dodecylpyrrolidone, gamma-butyrolacton and formamide, N, N- dimethylacetamide
The combination of amine, dimethyl sulfoxide and benzene, the combination of benzene, chlorobenzene, bromobenzene and benzonitrile, benzaldehyde, Ergol and benzyl ether
Combination, the combination of methanol, ethyl alcohol, isopropanol, acetone and butanone, N-Methyl pyrrolidone, n-vinyl pyrrolidone, N- ring
The combination of hexyl pyrrolidones, n-octylpyrrolidone and N-dodecylpyrrolidone, gamma-butyrolacton, formamide, N- methyl
Formamide, N,N-dimethylformamide, the combination dimethyl sulfoxide of DMAC N,N' dimethyl acetamide and dimethyl sulfoxide, benzene, chlorobenzene,
Bromobenzene, benzonitrile, benzaldehyde, Ergol and combination of benzyl ether etc..
Preferably, it is described be then sonicated in Vltrasonic device used be probe type Vltrasonic device or water-bath type Vltrasonic device；
Preferably, the ultrasonic power being then sonicated be 50W~1000W, such as 50W, 100W, 200W, 300W,
400W, 500W, 600W, 700W, 800W, 900W or 1000W etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable, preferably 100W~500W.
Preferably, the ultrasonic time being then sonicated be 0.5h~120h, such as 0.5h, 1h, 5h, 10h, 20h,
30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h, 110h or 120h etc., it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range, preferably 1h~50h.
Preferably, the concentration of two-dimensional material two-dimensional material in the dispersion liquid in redisperse agent be 0.01mg/mL~
100mg/mL, for example, 0.01mg/mL, 0.05mg/mL, 0.1mg/mL, 0.5mg/mL, 1mg/mL, 5mg/mL, 10mg/mL,
20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL or 100mg/mL etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 0.1mg/mL
~10mg/mL.
The two-dimensional material that the method is prepared through the invention can keep preferably dividing in a variety of redisperse agent
Performance is dissipated, the concentration of obtained dispersion liquid is also higher.
Preferably, the size of two-dimensional material two-dimensional material in the dispersion liquid in redisperse agent is 1nm~5000nm,
Such as 1nm, 10nm, 100nm, 500nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000nm, 3500nm, 4000nm,
4500nm or 5000nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable
With, preferably 1nm~500nm,.
Preferably, the two-dimensional material in the dispersion liquid in redisperse agent two-dimensional material with a thickness of 1 layer~10 layers, example
Such as 1 layer, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 8 layers, 9 layers or 10 layers, it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range.
Compared with prior art, the invention has the following advantages:
(1) two-dimensional material powder is made in such a way that ball grinding method, ultrasonic treatment combine precipitating in the method for the invention,
It is more easy compared with the prior art, and overcoming the two-dimensional material for being less than filter membrane for size present in existing filter method can not
Play the problem of efficiently separating；Meanwhile also overcoming that the duration in existing filter method is long, and what can not be mass produced asks
Topic；
(2) two-dimensional material powder made from the method for the invention good can disperse in multi-solvents, overcome
Powder can not effectively be dispersed to the problems in multi-solvents in the prior art, make two-dimensional material powder obtained in different solvents
The concentration of dispersion reaches as high as 100mg/mL.
Detailed description of the invention
Fig. 1 is raw materials used MoS in 1-5 of the embodiment of the present invention2Scanning electron microscope (SEM) photograph；
Fig. 2 is MoS obtained in the embodiment of the present invention 12The appearance photo of two-dimensional material powder；
Fig. 3 is MoS obtained in 1-5 of the embodiment of the present invention2Dispersion liquid of the two-dimensional material powder in different redisperse agent
Appearance photo；
Fig. 4 is MoS obtained in the embodiment of the present invention 12Two-dimensional material powder aqueous dispersions dilute 500 times after it is ultraviolet-
Visible absorption spectra figure；
Fig. 5 is raw materials used WS in the embodiment of the present invention 62Scanning electron microscope (SEM) photograph；
Fig. 6 is WS obtained in the embodiment of the present invention 62The appearance photo of two-dimensional material powder；
Fig. 7 is WS obtained in the embodiment of the present invention 62The appearance of two-dimensional material powder N,N-dimethylformamide dispersion liquid
Photo；
Fig. 8 is WS obtained in the embodiment of the present invention 62Two-dimensional material powder N,N-dimethylformamide dispersion liquid dilution 20
Uv-visible absorption spectra after times.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
Specific embodiment of the invention part provides two-dimensional material raw powder's production technology, and the method includes following steps
It is rapid:
(1) two-dimensional material raw material is subjected to ball milling, obtains solid material；
(2) just dispersion solvent is added in obtained solid material in step (1), carries out just ultrasonic treatment, obtains two-dimentional material
Expect the dispersion liquid in first dispersion solvent；
(3) precipitating reagent is added in the dispersion liquid in first dispersion solvent to two-dimensional material described in step (2), precipitating is complete
After be centrifuged and dry, obtain two-dimensional material powder.
Specific embodiment of the invention part additionally provides the preparation side of two-dimensional material powder dispersion made from the above method
Method, the method are as follows:
Above-mentioned two-dimensional material powder is added in redisperse agent, is then sonicated, obtains two-dimensional material in redisperse
Dispersion liquid in agent.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
Present embodiments provide a kind of MoS2Two-dimensional material raw powder's production technology, the described method comprises the following steps:
(1) the raw material MoS for being 5 μm by 1g average-size2(its scanning electron microscope is as shown in Figure 1), 2g grinding aid sodium chloride and
The agate ball that 10g diameter is 0.5mm mixes, and then ball milling 0.5h separates agate ball, gained samples with water is cleaned multiple times, directly
To washing sodium chloride completely to the greatest extent, vacuum drying obtains solid material；
(2) 1L just dispersion solvent N-Methyl pyrrolidone (NMP) is added in obtained solid material in step (1), with
The ultrasonic power ultrasound 12h of 100W, obtains MoS2Dispersion liquid in first dispersion solvent；
(3) MoS in step (2)21L precipitating reagent ethyl acetate is added in the dispersion liquid in first dispersion solvent, is filled to it
After fractional precipitation, 10min is centrifugated with the revolving speed of 2000r/min, sediment fraction is dried in vacuo, MoS is obtained2Two-dimensional material powder
Body.
The present embodiment additionally provides above-mentioned MoS2The preparation method of two-dimensional material powder aqueous dispersions, the method are as follows:
By the above-mentioned MoS of 0.1g2Two-dimensional material powder is added in 5mL redisperse agent water, with the power ultrasound 5h of 200W, obtains
MoS2Two-dimensional material powder aqueous dispersions, appearance photo are as shown in Figure 3.
MoS obtained2Two-dimensional material powder aqueous dispersions dilute uv-visible absorption spectra such as Fig. 4 institute after 500 times
Show, is calculated using Lambert-Beer law it is found that its concentration is about 9.85mg/mL.
Embodiment 2:
Present embodiments provide a kind of MoS2In two-dimensional material raw powder's production technology, the preparation method and embodiment 1
It is identical.
The present embodiment additionally provides above-mentioned MoS2The preparation method of two-dimensional material powder alcohol dispersion liquid, the method is such as
Under:
By the above-mentioned MoS of 0.1g2Two-dimensional material powder is added in 5mL redisperse agent ethyl alcohol, with the power ultrasound 5h of 200W, obtains
To MoS2Two-dimensional material powder alcohol dispersion liquid, appearance photo are as shown in Figure 3.
Embodiment 3:
Present embodiments provide a kind of MoS2In two-dimensional material raw powder's production technology, the preparation method and embodiment 1
It is identical.
The present embodiment additionally provides above-mentioned MoS2The preparation method of two-dimensional material powder acetone dispersion liquor, the method is such as
Under:
By the above-mentioned MoS of 0.1g2Two-dimensional material powder is added in 5mL redisperse agent acetone, with the power ultrasound 5h of 200W, obtains
To MoS2Two-dimensional material powder acetone dispersion liquor, appearance photo are as shown in Figure 3.
Embodiment 4:
Present embodiments provide a kind of MoS2In two-dimensional material raw powder's production technology, the preparation method and embodiment 1
It is identical.
The present embodiment additionally provides above-mentioned MoS2The preparation method of two-dimensional material powder n,N-Dimethylformamide dispersion liquid,
The method is as follows:
By the above-mentioned MoS of 0.1g2Two-dimensional material powder is added in 5mL redisperse agent n,N-Dimethylformamide, with 200W's
Power ultrasound 5h, obtains MoS2Two-dimensional material powder n,N-Dimethylformamide dispersion liquid, appearance photo are as shown in Figure 3.
Embodiment 5:
Present embodiments provide a kind of MoS2In two-dimensional material raw powder's production technology, the preparation method and embodiment 1
It is identical.
The present embodiment additionally provides above-mentioned MoS2The preparation method of two-dimensional material powder NMP dispersion liquid, the method are as follows:
By the above-mentioned MoS of 0.1g2Two-dimensional material powder is added in 5mL redisperse agent NMP, with the power ultrasound 5h of 200W, obtains
To MoS2The concentration of two-dimensional material powder is the MoS of 20mg/mL2Two-dimensional material powder NMP dispersion liquid, appearance photo such as Fig. 3 institute
Show.
It is can be seen that from embodiment 1-5 as shown in Figure 1, MoS used in embodiment 1-52The size of raw material is 1~10 μ
M, average-size are 5 μm.MoS obtained2The appearance photo of two-dimensional material powder is as shown in Fig. 2, MoS2Two-dimensional material powder is darkly
Color, sheet, and with glossy.
MoS made from embodiment 1-52Water, ethyl alcohol, acetone, N,N-dimethylformamide and the NMP of two-dimensional material powder points
The appearance photo of dispersion liquid is as shown in figure 3, it is in dirty-green.
Embodiment 6:
Present embodiments provide a kind of MoS2Two-dimensional material raw powder's production technology, the described method comprises the following steps:
(1) the raw material WS for being 2 μm by 1g average-size2(its scanning electron microscope is as shown in Figure 5), 1g grinding aid sodium carbonate and
The stainless steel ball that 100g diameter is 20mm mixes, and then ball milling 120h separates stainless steel ball, gained samples with water is repeatedly clear
It washes, until sodium carbonate is washed completely to the greatest extent, vacuum drying obtains solid material；
(2) 10mL just dispersion solvent N-Methyl pyrrolidone (NMP) is added in obtained solid material in step (1), with
The ultrasonic power ultrasound 0.5h of 1000W, obtains WS2Dispersion liquid in first dispersion solvent；
(3) WS in step (2)240mL precipitating reagent Ethyl formate is added in the dispersion liquid in first dispersion solvent, to it
Sufficiently after precipitating, 40min is centrifugated with the revolving speed of 5000r/min, sediment fraction is dried in vacuo, WS is obtained2Two-dimensional material
Powder.
The present embodiment additionally provides above-mentioned WS2The preparation method of two-dimensional material powder DMF dispersion liquid, the method are as follows:
By the above-mentioned MoS of 0.05g2Two-dimensional material powder is added in 50mL redisperse agent n,N-Dimethylformamide (DMF), with
The power ultrasound 1h of 1000W, obtains WS2Two-dimensional material powder DMF dispersion liquid, appearance photo are as shown in Figure 7.
Fig. 5 is WS in embodiment 62The stereoscan photograph of raw material, it is seen that it is having a size of 1 μm~10 μm, average-size 2
μm.Fig. 6 is WS prepared by embodiment 62The appearance photo of two-dimensional material powder is black, in the form of sheets, and with glossy.
Fig. 7 is WS prepared by embodiment 62Two-dimensional material DMF dispersion liquid appearance photo, WS2Two-dimensional material DMF dispersion liquid is in kermesinus.
Fig. 7 is WS prepared by embodiment 62Two-dimensional material aqueous dispersions dilute the uv-visible absorption spectra after 20 times, utilize orchid primary
Spy-Beer law calculates it is found that its concentration is about 0.56mg/mL.
Embodiment 7:
A kind of graphite two-dimensional material raw powder's production technology is present embodiments provided, the described method comprises the following steps:
It (1) is 6mm's by raw graphite, 0.1g grinding aid calcium carbonate and 10g diameter that 0.01g average-size is 100 μm
Then zirconia balls mixing, ball milling 20h separate zirconia balls, gained sample is cleaned multiple times with hydrochloric acid, until by carbonic acid
Calcium is washed to the greatest extent completely, then is cleaned multiple times with water, remaining hydrochloric acid is washed completely to the greatest extent, and vacuum drying obtains solid material；
(2) 1mL just dispersion solvent dimethyl sulfoxide (DMSO) is added in obtained solid material, in step (1) with 200W
Ultrasonic power ultrasound 5h, obtain dispersion liquid of the graphite in first dispersion solvent；
(3) 100mL precipitating reagent ethyl acetate is added in graphite in the dispersion liquid in first dispersion solvent in step (2), to
After it is sufficiently precipitated, 20min is centrifugated with the revolving speed of 10000r/min, sediment fraction is dried in vacuo, obtains graphite two dimension
Material powder.
The present embodiment additionally provides the preparation method of above-mentioned graphite two-dimensional material powder acetone dispersion liquor, and the method is such as
Under:
The above-mentioned graphite two-dimensional material powder of 0.005g is added in 5mL redisperse agent acetone, with the power ultrasound of 300W
12h obtains graphite two-dimensional material powder acetone dispersion liquor, concentration 100mg/mL.
Embodiment 8:
A kind of h-BN two-dimensional material raw powder's production technology is present embodiments provided, the described method comprises the following steps:
(1) by 1g average-size be 0.1 μm raw material h-BN, 10g grinding aid ammonium chloride and 50g diameter be 3mm nitridation
Then silicon ball mixing, ball milling 10h separate silicon nitride ball, gained samples with water is cleaned multiple times, until ammonium chloride is washed completely
To the greatest extent, vacuum drying, obtains solid material；
(2) 50mL just dispersion solvent n,N-Dimethylformamide is added in obtained solid material, in step (1) with 400W
Ultrasonic power ultrasound 3h, obtain dispersion liquid of the h-BN in first dispersion solvent；
(3) 100mL precipitating reagent methyl formate is added in h-BN in the dispersion liquid in first dispersion solvent in step (2), to
After it is sufficiently precipitated, 30min is centrifugated with the revolving speed of 5000r/min, sediment fraction is dried in vacuo, h-BN two dimension material is obtained
Feed powder body.
The present embodiment additionally provides the preparation method of above-mentioned h-BN two-dimensional material powder NMP dispersion liquid, and the method is as follows:
The above-mentioned h-BN two-dimensional material powder of 0.3g is added in 50mL redisperse agent acetone, for 24 hours with the power ultrasound of 600W,
Obtain h-BN two-dimensional material powder NMP dispersion liquid.
Embodiment 9:
A kind of two selenizing molybdenum two-dimensional material raw powder's production technologies are present embodiments provided, the method includes following steps
It is rapid:
(1) by 0.5g average-size be 0.2 μm two selenizing molybdenum of raw material and 30g diameter be 3mm silicon nitride ball mix, ball
10h is ground, the hard tungsten-carbide ball mixing of 14mm is added, then ball milling ball is separated, is dried in vacuo, obtains solid by ball milling 7h
Material；
(2) 50mL just dispersion solvent N-METHYLFORMAMIDE is added in obtained solid material, in step (1) with the super of 250W
Acoustical power ultrasound 10h obtains dispersion liquid of the two selenizing molybdenums in first dispersion solvent；
(3) 10mL precipitating reagent ethyl acetate is added in two selenizing molybdenums in the dispersion liquid in first dispersion solvent in step (2),
After it is sufficiently precipitated, 60min is centrifugated with the revolving speed of 2500r/min, sediment fraction is dried in vacuo, two selenizing molybdenums are obtained
Two-dimensional material powder.
The present embodiment additionally provides the preparation method of above-mentioned two selenizings molybdenum two-dimensional material powder DMSO dispersion liquid, the method
It is as follows:
The above-mentioned two selenizings molybdenum two-dimensional material powder of 0.2g is added in 10mL redisperse agent acetone, with the power ultrasound of 800W
20h obtains two selenizing molybdenum two-dimensional material powder DMSO dispersion liquids.
Integrated embodiment 1-9 can be seen that the side that the method for the invention combines precipitating by ball grinding method, ultrasonic treatment
Two-dimensional material powder is made in formula, more easy compared with the prior art, overcomes small for size present in existing filter method
It can not be played the problem of efficiently separating in the two-dimensional material of filter membrane；Meanwhile it is long to also overcome the duration in existing filter method,
The problem of can not being mass produced.
Also, two-dimensional material powder made from the method for the invention good can disperse in multi-solvents, overcome
Powder can not effectively be dispersed to the problems in multi-solvents in the prior art, make two-dimensional material powder obtained in different solvents
The concentration of middle dispersion reaches as high as 100mg/mL.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (43)
1. two-dimensional material raw powder's production technology, which is characterized in that the described method comprises the following steps:
(1) two-dimensional material raw material is subjected to ball milling, obtains solid material；
(2) just dispersion solvent is added in obtained solid material in step (1), carries out just ultrasonic treatment, obtains two-dimensional material and exist
Dispersion liquid in first dispersion solvent；
(3) precipitating reagent is added in the dispersion liquid in first dispersion solvent to two-dimensional material described in step (2), precipitating is completely laggard
Row centrifuge separation or filtering obtain two-dimensional material powder after dry；
Just dispersion solvent is N-Methyl pyrrolidone, n-vinyl pyrrolidone, N- cyclohexyl pyrrolidines described in step (2)
Ketone, n-octylpyrrolidone, N-dodecylpyrrolidone, gamma-butyrolacton, formamide, N-METHYLFORMAMIDE, N, N- dimethyl
Any one in formamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide or at least two combination；
Precipitating reagent described in step (3) is methyl formate, Ethyl formate, propyl formate, methyl acetate, ethyl acetate, acetic acid third
In ester, methyl propionate, ethyl propionate, propyl propionate, methanol, ethyl alcohol, isopropanol, n-hexane, normal heptane, normal octane or petroleum ether
Any one or at least two combination；
Step (1) it is described by two-dimensional material raw material carry out ball milling specific method the following steps are included:
(a) two-dimensional material raw material and ball milling ball are mixed, carries out ball milling；
(b) it is dried in vacuo after separating the solid material after ball milling in step (a) with ball milling ball, obtains solid material；
Or
(a ') mixes two-dimensional material raw material, grinding aid and ball milling ball, carries out ball milling；
After (b ') separates the solid material after ball milling in step (a ') with ball milling ball, it is molten that washing is added into the material after separation
Agent is washed, and vacuum drying obtains solid material；
Grinding aid described in step (a ') is by anion and cation composition, wherein cation is cation, the IIA of IA race element
Race's element cation or ammonium root cation in any one or at least two combination, anion be hydroxide ion, nitric acid
Radical ion, sulfate ion, hydrogen sulfate ion, phosphate anion, phosphoric acid hydrogen radical ion, dihydrogen phosphate ions, carbonate
Any one in ion, bicarbonate ion or citrate ion or at least two combination.
2. preparation method according to claim 1, which is characterized in that step (1) the two-dimensional material raw material is graphite, six
Any one in square boron nitride, molybdenum disulfide, tungsten disulfide, two selenizing molybdenums or two tungsten selenides or at least two combination.
3. preparation method according to claim 1, which is characterized in that the size of step (1) the two-dimensional material raw material is
0.1 μm~100 μm.
4. preparation method according to claim 3, which is characterized in that the size of step (1) the two-dimensional material raw material is
0.5 μm~10 μm.
5. preparation method according to claim 1, which is characterized in that step (a) and ball milling ball described in step (a ')
Material is independently any one in agate, zirconium dioxide, stainless steel, modulation steel, hard tungsten carbide, silicon nitride or alundum
Kind or at least two combination.
6. preparation method according to claim 1, which is characterized in that step (a) and ball milling ball described in step (a ')
Diameter is independently 0.5mm~20mm.
7. preparation method according to claim 1, which is characterized in that ball milling described in step (a) and step (a ') when
Between be independently 0.5h~120h.
8. preparation method according to claim 7, which is characterized in that ball milling described in step (a) and step (a ') when
Between be independently 1h~50h.
9. preparation method according to claim 1, which is characterized in that step (a) and ball milling ball described in step (a ')
Additional amount is independently 1 times~1000 times of the two-dimensional material material quality.
10. preparation method according to claim 9, which is characterized in that step (a) and ball milling ball described in step (a ')
Additional amount is independently 50 times~300 times of the two-dimensional material material quality.
11. preparation method according to claim 1, which is characterized in that the additional amount of grinding aid described in step (a ') is
0 times of the two-dimensional material material quality~100 times and do not include 0 times.
12. preparation method according to claim 11, which is characterized in that the additional amount of grinding aid described in step (a ') is
1 times of the two-dimensional material material quality~30 times.
13. preparation method according to claim 1, which is characterized in that cleaning solvent described in step (b ') is water, salt
Any one in acid, sulfuric acid or nitric acid or at least two combination.
14. preparation method according to claim 1, which is characterized in that washed described in step (b ') are as follows: by the ball milling
The grinding aid in solid material afterwards washes completely.
15. preparation method according to claim 1, which is characterized in that step (b) and vacuum drying temperature described in (b ')
Degree is independently 0 DEG C~100 DEG C.
16. preparation method according to claim 15, which is characterized in that vacuum drying described in step (b) and (b ')
Temperature is independently 20 DEG C~60 DEG C.
17. preparation method according to claim 1, which is characterized in that the ultrasound in being just ultrasonically treated described in step (2)
Device is probe type Vltrasonic device and/or water-bath type Vltrasonic device.
18. preparation method according to claim 1, which is characterized in that the ultrasonic function being just ultrasonically treated described in step (2)
Rate is 50W~1000W.
19. preparation method according to claim 18, which is characterized in that the ultrasound being just ultrasonically treated described in step (2)
Power is 100W~500W.
20. preparation method according to claim 1, which is characterized in that when the ultrasound being just ultrasonically treated described in step (2)
Between be 0.5h~120h.
21. preparation method according to claim 20, which is characterized in that the ultrasound being just ultrasonically treated described in step (2)
Time is 1h~50h.
22. preparation method according to claim 1, which is characterized in that two-dimensional material described in step (2) just disperse it is molten
The concentration of two-dimensional material is 0.01mg/mL~100mg/mL in dispersion liquid in agent.
23. preparation method according to claim 22, which is characterized in that two-dimensional material described in step (2) is dispersed just
The concentration of two-dimensional material is 0.1mg/mL~10mg/mL in dispersion liquid in solvent.
24. preparation method according to claim 1, which is characterized in that the additional amount of precipitating reagent described in step (3) are as follows:
The volume ratio of the precipitating reagent and dispersion liquid of the two-dimensional material in first dispersion solvent is 1:(0.01~100).
25. preparation method according to claim 24, which is characterized in that the additional amount of precipitating reagent described in step (3) are as follows:
The volume ratio of the precipitating reagent and dispersion liquid of the two-dimensional material in first dispersion solvent is 1:(0.5~10).
26. preparation method according to claim 1, which is characterized in that the revolving speed of centrifuge separation described in step (3) is
500r/min~10000r/min.
27. preparation method according to claim 26, which is characterized in that the revolving speed of centrifuge separation described in step (3) is
1000r/min~6000r/min.
28. preparation method according to claim 1, which is characterized in that the centrifugation time of centrifuge separation described in step (3)
For 1min~120min.
29. preparation method according to claim 28, which is characterized in that when the centrifugation of centrifuge separation described in step (3)
Between be 5min~60min.
30. preparation method according to claim 1, which is characterized in that filter membrane used or filter in filtering described in step (3)
The aperture of paper is 1 μm~100 μm.
31. preparation method according to claim 1, which is characterized in that dry for vacuum drying, liter described in step (3)
Temperature is dry or freeze-drying in any one or at least two combination.
32. the preparation method of two-dimensional material powder dispersion, which is characterized in that the method are as follows:
The two-dimensional material powder that any one of claim 1-31 is prepared is added in redisperse agent, is then sonicated,
Obtain dispersion liquid of the two-dimensional material in redisperse agent.
33. preparation method according to claim 32, which is characterized in that the redisperse solvent be water, methanol, ethyl alcohol,
Isopropanol, acetone, butanone, N-Methyl pyrrolidone, n-vinyl pyrrolidone, N- cyclohexyl pyrrolidone, N- octyl pyrroles
Alkanone, N-dodecylpyrrolidone, gamma-butyrolacton, formamide, N-METHYLFORMAMIDE, N,N-dimethylformamide, N, N- bis-
Any one in methylacetamide, dimethyl sulfoxide, benzene, chlorobenzene, bromobenzene, benzonitrile, benzaldehyde, Ergol or benzyl ether
Or at least two combination.
34. preparation method according to claim 32, which is characterized in that it is described be then sonicated in Vltrasonic device used be
Probe type Vltrasonic device or water-bath type Vltrasonic device.
35. preparation method according to claim 32, which is characterized in that the ultrasonic power being then sonicated is 50W
~1000W.
36. preparation method according to claim 35, which is characterized in that the ultrasonic power being then sonicated is 100W
~500W.
37. preparation method according to claim 32, which is characterized in that the ultrasonic time being then sonicated is 0.5h
~120h.
38. the preparation method according to claim 37, which is characterized in that the ultrasonic time being then sonicated be 1h~
50h。
39. preparation method according to claim 32, which is characterized in that dispersion of the two-dimensional material in redisperse agent
The concentration of two-dimensional material is 0.01mg/mL~100mg/mL in liquid.
40. preparation method according to claim 39, which is characterized in that dispersion of the two-dimensional material in redisperse agent
The concentration of two-dimensional material is 0.1mg/mL~10mg/mL in liquid.
41. preparation method according to claim 32, which is characterized in that dispersion of the two-dimensional material in redisperse agent
The size of two-dimensional material is 1nm~5000nm in liquid.
42. preparation method according to claim 41, which is characterized in that dispersion of the two-dimensional material in redisperse agent
The size of two-dimensional material is 1nm~500nm in liquid.
43. preparation method according to claim 32, which is characterized in that dispersion of the two-dimensional material in redisperse agent
Two-dimensional material with a thickness of 1 layer~10 layers in liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710037954.3A CN106830084B (en) | 2017-01-19 | 2017-01-19 | The preparation method of two-dimensional material powder and its dispersion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710037954.3A CN106830084B (en) | 2017-01-19 | 2017-01-19 | The preparation method of two-dimensional material powder and its dispersion liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106830084A CN106830084A (en) | 2017-06-13 |
| CN106830084B true CN106830084B (en) | 2019-02-12 |
Family
ID=59124189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710037954.3A Active CN106830084B (en) | 2017-01-19 | 2017-01-19 | The preparation method of two-dimensional material powder and its dispersion liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106830084B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117590B (en) * | 2017-06-14 | 2019-01-29 | 合肥工业大学 | A kind of method that gradient sphere grinding prepares two-dimentional black phosphorus |
| JP6651185B2 (en) * | 2018-02-27 | 2020-02-19 | 国立大学法人東京工業大学 | Inorganic particle composite, method for producing the same, and inorganic particle composite dispersion |
| CN111212812A (en) * | 2017-10-12 | 2020-05-29 | 国立大学法人东京工业大学 | Inorganic particle composite, method for producing same, and inorganic particle composite dispersion liquid |
| TWI666167B (en) * | 2018-08-21 | 2019-07-21 | 國立臺灣科技大學 | Production method of low dimensional nano-material |
| CN109319841A (en) * | 2018-09-30 | 2019-02-12 | 华南理工大学 | A kind of preparation method of the two-dimension nano materials of heterojunction structure |
| CN110064575A (en) * | 2019-04-25 | 2019-07-30 | 国家纳米科学中心 | A kind of two-dimensional material solid lubricating film and preparation method thereof |
| CN110526293B (en) * | 2019-09-09 | 2021-02-19 | 北京化工大学 | Method for preparing two-dimensional nano material by aid of easily decomposed salt |
| CN111233031B (en) * | 2020-01-19 | 2022-08-02 | 国家纳米科学中心 | Perovskite quantum dot and preparation method thereof |
| CN111196611A (en) * | 2020-01-19 | 2020-05-26 | 国家纳米科学中心 | Two-dimensional nanosheet and preparation method thereof |
| WO2023190637A1 (en) * | 2022-03-30 | 2023-10-05 | 京セラ株式会社 | Carbon composite material and dispersion liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105253862A (en) * | 2014-07-15 | 2016-01-20 | 中国科学院过程工程研究所 | Method for large-scale preparation of graphene-like boron nitride nano-sheets through high temperature liquid-phase peeling |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671015B (en) * | 2009-10-13 | 2011-07-20 | 南昌航空大学 | Method of producing graphene |
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
| CN102452649B (en) * | 2010-10-18 | 2014-04-02 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene |
| CN102757038B (en) * | 2011-04-28 | 2014-02-26 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene |
| CN102618107B (en) * | 2012-03-31 | 2014-10-08 | 深圳市贝特瑞纳米科技有限公司 | Conductive graphite cream and preparation method thereof |
| CN103935998B (en) * | 2014-05-09 | 2016-04-13 | 中国科学院上海微***与信息技术研究所 | A kind of preparation method of graphene aqueous solution |
| CN104030281B (en) * | 2014-06-25 | 2016-04-13 | 南昌大学 | A kind of preparation method of Graphene |
| CN105502371B (en) * | 2016-01-05 | 2018-01-19 | 上海和伍复合材料有限公司 | A kind of liquid phase strip preparation method of graphene |
| CN105752977B (en) * | 2016-04-29 | 2017-12-12 | 江苏超电新能源科技发展有限公司 | A kind of technology of preparation method of high conductivity graphene powder |
| CN106115679A (en) * | 2016-07-04 | 2016-11-16 | 济南大学 | A kind of low cost prepares the method for Graphene |
| CN106219608B (en) * | 2016-07-06 | 2017-11-21 | 中山大学 | A kind of preparation method of two-dimensional material |
-
2017
- 2017-01-19 CN CN201710037954.3A patent/CN106830084B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105253862A (en) * | 2014-07-15 | 2016-01-20 | 中国科学院过程工程研究所 | Method for large-scale preparation of graphene-like boron nitride nano-sheets through high temperature liquid-phase peeling |
Non-Patent Citations (1)
| Title |
|---|
| Improved dispersant-free liquid exfoliation down to the grapheme-like state of solvent-free machanochemically delaminated bulk MoS2;Oleg Yu.Posudievsky et al.;《Journal of Materials Chemistry C》;20130808;6411-6415 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106830084A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106830084B (en) | The preparation method of two-dimensional material powder and its dispersion liquid | |
| CN105110318B (en) | A kind of graphene water paste and preparation method thereof | |
| CN107200318A (en) | Two-dimensional material quantum piece and preparation method thereof | |
| CN105821227B (en) | A kind of method for preparing graphene enhancing Cu-base composites | |
| CN106564885B (en) | A kind of continuous fluidic device and its method for preparing graphene | |
| Yousef et al. | A new strategy for functionalization of char derived from pyrolysis of textile waste and its application as hybrid fillers (CNTs/char and graphene/char) in cement industry | |
| CN105347328A (en) | Method for preparing monodisperse carbon microspheres by using cane sugar as carbon source | |
| CN103819760B (en) | A kind of processing method preparing high-performance carbon black rubber master batch | |
| CN106582994B (en) | A kind of device and production method continuously preparing graphene slurry | |
| CN107301922B (en) | Three-dimensional porous graphene nano material and its preparation method and application | |
| CN105523549B (en) | A kind of remover and application that graphene is prepared for mechanical stripping method | |
| CN107879332A (en) | The method that space-time synchronous ultrasound ball-milling method peels off preparing graphite alkene | |
| CN110143586A (en) | A kind of preparation method of the graphene of single layer or few layer | |
| CN105712404B (en) | A kind of MoS2The preparation method of quantum dot | |
| CN103043675A (en) | Preparation method of Eamonn mixed layer clay micro-manometer material | |
| CN103641172A (en) | Method for preparing nanometer layered molybdenum disulfide | |
| CN105271175A (en) | Dispersion method of carbon nano tube | |
| CN102689911A (en) | Preparation method of ZSM-5 molecular sieve nanosphere with multi-level pore hollow structure | |
| CN106032587B (en) | A kind of amido enhancing graphene fiber and preparation method thereof | |
| Sun et al. | Controlled synthesis of Sn doped ZnO microspheres stringed on carbon fibers with enhanced visible-light photocatalytic activities | |
| CN106391122A (en) | A synthetic method of a polypyrrole-functionalized cobalt complex composite material and applications of the material | |
| CN108163894A (en) | A kind of ultrahigh concentration stripping means of transient metal sulfide | |
| CN109904451A (en) | A kind of graphene composite material and its preparation method and application | |
| CN104071785A (en) | Method for preparing graphene with three-dimensional macroscopic porous structure | |
| CN105602529B (en) | It is a kind of using sawdust as the preparation method of the sizing phase-change material of backing material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |