CN106830084A - 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
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- 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
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Abstract
The invention provides two-dimensional material powder and its preparation method of dispersion liquid, the described method comprises the following steps：Two-dimensional material raw material is carried out into ball milling, solid material is obtained；Dispersion solvent at the beginning of to being added in gained solid material, it is ultrasonically treated at the beginning of carrying out, obtain dispersion liquid of the two-dimensional material in first dispersion solvent；It is centrifuged and dries to after adding precipitating reagent, precipitation complete in dispersion liquid of the two-dimensional material in first dispersion solvent, obtains two-dimensional material powder.The preparation method of two-dimensional material powder dispersion is：By in the addition redisperse agent of two-dimensional material powder, it is then sonicated, is obtained dispersion liquid of the two-dimensional material in redisperse agent.Compared with the conventional method, this method has wide material sources, and the advantages of 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, it is related to the preparation side of two-dimensional material powder and its dispersion liquid
Method.
Background technology
Two-dimensional material with Graphene as representative, due to its there is the characteristics such as prominent light, electricity, sensing and energy stores and
Receive much concern.In recent years, study more two-dimensional material and be mainly Graphene and class grapheme two-dimension material.Wherein, more allusion quotation
The class grapheme two-dimension material of type has the chalcogenide of transition metal two, such as MoS2And WS2Deng by IVB in the periodic table of elements, VB,
The layer structure of the sulfur family nonmetalloids such as the transition metal and S, Se and Te of VIB, VIIB and VIII element composition.Additionally,
Class grapheme two-dimension material also BN (h-BN) comprising hexagonal structure etc..
So far, the powder two-dimensional material of the two-dimensional material reported for work in document and patent has many special property,
The increasing research interest of people is caused, how to have realized that the scale of individual layer or few layer two-dimensional material prepares nature and just turns into
Current study hotspot.At this stage, the preparation of two-dimensional material still there are problems that the following：First, prepare with scale two dimension
Material often destroys its intrinsic structure；Secondly, substantial amounts of solvent is used during two-dimensional material is prepared, while also needing to
Extra to add such as surfactant to promote the stripping of two-dimensional material, final product is often with the shape of two-dimensional material dispersion liquid
Formula is present.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 additive such as surfactant can make preparation work
Skill is complicated, even if a small amount of residual can also largely effect on its performance.Therefore, the preparation of exploitation two-dimensional material powder and its dispersion liquid
Method has great theory and realistic meaning.
The main policies of two-dimensional material prepare with scale be by two-dimensional material in specific solvent by ultrasound, cut at a high speed
Cut or the additional physical mechanical effect stripping such as ball milling is prepared from, from the angle of its dispersion solvent, can be classified as organic
Polar solvent and the major class of water two.Wherein, to be primarily referred to as selection close with two-dimensional material surface tension organic for organic polar solvent
Solvent, such as NMP and DMF.A kind of method that J.N.Coleman et al. have studied utilization ultrasonic disperse and centrifugation, obtains
MoS2、WS2And MoSe2Etc. NMP dispersion liquids (the Two-dimensional nanosheets produced by of two-dimensional material
liquid exfoliation oflayered materials.J.N.Coleman,et al.Science,2011,331:
568-571.).Y.Hernandez et al. selection flaky graphites are raw material, by ultrasonic disperse and centrifugation, obtain stone
NMP dispersion liquids (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.).This kind of method can be with the intrinsic two-dimensional material of the few Rotating fields of very effective 1~10 layer of acquisition, but high boiling solvent
Use, limit further applying for two-dimensional material；Meanwhile, the using of a large amount of organic solvents causes turning in course of industrialization
Fortune cost and risk are all greatly promoted.CN 104495828A disclose a kind of method that liquid phase stripping method prepares Graphene, its profit
With surfactants such as sodium taurocholate, lauryl sodium sulfate and neopelexes, by ultrasonic disperse, graphite is obtained
The aqueous dispersions of alkene.CN 103910354A disclose a kind of method that scale water mutually prepares Graphene, and it utilizes and contains hydrogen-oxygen
Change the alkaline aqueous solution of sodium, potassium hydroxide, lithium hydroxide and sodium carbonate etc., by ultrasonic disperse, be finally obtained Graphene
Aqueous dispersions.Dispersant such as surfactant is used so that need additionally to add cleaning step in preparation process, while residual
The dispersant for staying may have a huge impact to 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 disclose a kind of stabilization graphene colloid dispersion solution
Preparation method, it first passes through improved Hummer ' s methods and prepares graphene oxide, and further reduction is so as to obtain Graphene.But
This method obtains redox graphene colloidal dispersion, and its quality cannot compare favourably with Graphene.
After two-dimensional material dispersion liquid is prepared, the usual way of powder is obtained for vacuum filtration and drying, it is only a small amount of special
The dried powder of profit report can disperse back in organic solvent again.CN 103723708A disclose a kind of single-layer graphene to be had
Machine solution manufacturing method, methods described obtains graphene dispersing solution by ultrasonic disperse in organic solvent, then by taking out
Filter, washing and drying, can obtain Graphene solid powder.This amount of powder can be dispersed again in organic solvent by ultrasound
In.CN 104556020A disclose a kind of preparation method of Graphene alcohol dispersion liquid, and graphite is first added to N- methyl pyrroles by it
Ultrasound is carried out in pyrrolidone and peels off the dispersion liquid that Graphene is obtained with centrifugation, the graphene powder after filtering and drying
Can be re-dispersed into ethanol, repeat filtering and redisperse, the alcohol dispersion liquid of Graphene may finally be obtained.Although above-mentioned side
Method is more effective, but still there are problems that.Two-dimensional material firstly, for size less than filter membrane, such as two-dimensional material amount
Son point and quantum piece etc., suction filtration cannot play effective effect；Secondly, suction filtration process duration is more long, greatly limit
Large-scale production is made；Finally, dried powder whether effectively can be dispersed to again in multi-solvents be all the time it is outstanding and
Pending problem.
, there is following common problem in body and its multi-solvent dispersion liquid and preparation method thereof：Such as complex process, relatively costly and consumption
When it is more long etc., and the demand of large-scale production cannot be met.This is just in the urgent need to Devoting Major Efforts To Developing is simple, efficient and inexpensive
Universal method, the breakthrough for preparing on two-dimensional material powder and its dispersion liquid, and preparation method will certainly greatly accelerate it
Process of industrialization.
The content of the invention
It is relatively costly for complex process present in prior art, take it is more long, and two-dimensional material powder with its not
With the poor universality in solvent dispersions and be difficult to the problem of large-scale production, the invention provides two-dimensional material powder and
The preparation method of its dispersion liquid.The method of the invention has wide material sources, the advantages of easy to operate, prepared two-dimensional material
Powder sample is respectively provided with good dispersive property in multi-solvents, and the concentration of its dispersion liquid is higher, for the reality of two-dimensional material
Border is applied and large-scale production has important application value.
It is that, up to this purpose, the present invention uses following technical scheme：
In a first aspect, the invention provides two-dimensional material raw powder's production technology, the described method comprises the following steps：
(1) two-dimensional material raw material is carried out into ball milling, obtains solid material；
(2) to just dispersion solvent is added in gained solid material in step (1), carry out just ultrasonically treated, obtain two-dimentional material
Expect the dispersion liquid in first dispersion solvent；
(3) to precipitating reagent is added in dispersion liquid of the two-dimensional material in first dispersion solvent described in step (2), precipitation is complete
After be centrifuged or filter, obtain two-dimensional material powder after drying.
In the present invention, it is that the solid material that step (1) is obtained is entered that two-dimensional material is carried out into just ultrasonically treated purpose
Row ultrasound is peeled off.
It is that two-dimensional material powder is prepared by precipitation by the purpose that two-dimensional material carries out precipitation process in the present invention
Body, to overcome and cannot play the problem for efficiently separating less than the two-dimensional material of filter membrane for size present in existing filter method；
Meanwhile, the duration is long in also overcoming existing filter method, it is impossible to the problem of large-scale production.
It is following as currently preferred technical scheme, but not as the present invention provide technical scheme limitation, pass through
Following technical scheme, can preferably reach and realize technical purpose of the invention and beneficial effect.
Used as currently preferred technical scheme, step (1) the two-dimensional material raw material is graphite, hexagonal boron nitride, two
In molybdenum sulfide, tungsten disulfide, two selenizing molybdenums or two tungsten selenides any one 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 bisuphide 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 bisuphide, molybdenum bisuphide, 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 bisuphide, 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
Other unrequited numerical value are equally applicable in value, the number range, 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 scheme, step (1) specific method that two-dimensional material raw material is carried out ball milling
Comprise the following steps：
A () mixes two-dimensional material raw material and ball milling ball, carry out ball milling；
B () is vacuum dried after the solid material after ball milling in step (a) is separated with ball milling ball, obtain 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, washed to being added in the material after separation
Solvent is washed, is washed, vacuum drying obtains solid material.
In the present invention, generally when less than 1 μm two-dimensional material is prepared, it is necessary to add the grinding aid to carry out ball as adjuvant
Mill.
Used as currently preferred technical scheme, the material of ball milling ball is independent described in step (a) and step (a ')
For in agate, zirconium dioxide, stainless steel, modulation steel, hard tungsten carbide, silicon nitride or alundum any one or at least two
Combination, combination typical case but non-limiting examples have：The group of the combination of agate and zirconium dioxide, stainless steel and modulation steel
Close, 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, the combination of stainless steel, modulation steel, hard tungsten carbide and silicon nitride, modulation steel, hard tungsten carbide, silicon nitride and burning
Tie the combination of corundum, combination of agate, zirconium dioxide, stainless steel, modulation steel, hard tungsten carbide and silicon nitride etc..
Preferably, step (a) and the diameter of ball milling ball described in step (a ') are independently 0.5mm~20mm, for example
0.5mm, 1mm, 3mm, 5mm, 7mm, 10mm, 13mm, 15mm, 17mm or 20mm etc., it is not limited to cited numerical value, should
Other unrequited numerical value are equally applicable in number range.
Preferably, step (a) and the time of ball milling described in step (a ') are independently 0.5h~120h, for example
0.5h, 1h, 5h, 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h, 110h or 120h etc., it is not limited to
Other unrequited numerical value are equally applicable in cited numerical value, the number range, preferably 1h~50h.
Preferably, step (a) and the addition of ball milling ball described in step (a ') are independently the former two-dimensional material
Material 1 times~1000 times of 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 other unrequited numbers in cited numerical value, the number range
Value is equally applicable, preferably 50 times~300 times.
Preferably, the addition of grinding aid described in step (a ') is 0 times~100 times of the two-dimensional material material quality
And do 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 other unrequited numerical value are equally applicable in cited numerical value, the number range, preferably 1 times~
30 times.
Preferably, by anion and cation composition, its cationic is IA races element to grinding aid described in step (a ')
Cation, the cation of Group IIA element or ammonium root cation in any one or at least two combination, wherein IA races element
Cation in lithium ion, sodium ion, potassium ion, rubidium ion or cesium ion any one or at least two combination, Group IIA
The cation of element be beryllium ion, magnesium ion, calcium ion, strontium ion or barium ions in any one or at least two combination；
Anion is hydroxide ion, chlorion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate anion, phosphoric acid
In hydrogen radical ion, dihydrogen phosphate ions, carbanion, bicarbonate ion or citrate ion any one or at least
Two kinds of combination, the combination is typical but non-limiting examples have：The combination of hydroxide ion and chlorion, 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, chlorion, nitrate ion, sulfate ion and hydrogen sulfate ion
Combination, hydrogen sulfate ion, phosphate anion, phosphoric acid hydrogen radical ion, dihydrogen phosphate ions, carbanion, bicarbonate
Combination of radical ion and citrate ion etc..
Preferably, cleaning solvent described in step (b ') be water, hydrochloric acid, sulfuric acid or nitric acid in any one or at least two
Combination, combination typical case but non-limiting examples have：The sulphur of the aqueous hydrochloric acid solution of hydrochloric acid and water composition, sulfuric acid and water composition
The nitre aqueous acid of aqueous acid, nitric acid and water composition, the combination of hydrochloric acid and sulfuric acid, the combination of sulfuric acid and nitric acid, hydrochloric acid,
Combination of sulfuric acid and nitric acid etc..
Preferably, washing is described in step (b ')：Grinding aid in solid material after the ball milling is cleaned 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
Other unrequited numerical value are equally applicable in value, the number range, preferably 20 DEG C~60 DEG C.
Used as currently preferred technical scheme, just dispersion solvent is 1-METHYLPYRROLIDONE, N- second described in step (2)
Vinyl pyrrolidone, N- cyclohexyl pyrrolidones, NOP, N-dodecylpyrrolidone, gamma-butyrolacton, first
In acid amides, N-METHYLFORMAMIDE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide (DMSO) any one or extremely
Few two kinds combination, the combination is typical but non-limiting examples have：1-METHYLPYRROLIDONE and NVP
The group of combination, the combination of N- cyclohexyl pyrrolidones and NOP, N-dodecylpyrrolidone and gamma-butyrolacton
Close, the combination of formamide and N-METHYLFORMAMIDE, the combination of DMF and DMA, N, N- bis-
The combination of methylacetamide and dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, NVP and N- cyclohexyl pyrrolidines
The combination of ketone, the combination of NOP, N-dodecylpyrrolidone, gamma-butyrolacton and formamide, formamide, N-
The combination of NMF, DMF and DMA, gamma-butyrolacton, formamide, N- methyl first
The combination of acid amides, DMF, DMA and dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, N- second
Vinyl pyrrolidone, N- cyclohexyl pyrrolidones, NOP, N-dodecylpyrrolidone, gamma-butyrolacton and first
Combination of acid amides etc..
Preferably, described in step (2) just it is ultrasonically treated in Vltrasonic device be probe type Vltrasonic device and/or water-bath type
Vltrasonic device.
Preferably, just ultrasonically treated ultrasonic power is 50W~1000W described in step (2), such as 50W, 100W,
200W, 300W, 400W, 500W, 600W, 700W, 800W, 900W or 1000W etc., it is not limited to cited numerical value, should
Other unrequited numerical value are equally applicable in number range, preferably 100W~500W.
Preferably, just ultrasonically treated ultrasonic time is 0.5h~120h described in step (2), 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
Other unrequited numerical value are equally applicable in value, the number range, preferably 1h~50h.
Preferably, the concentration of two-dimensional material is in dispersion liquid of the two-dimensional material in first dispersion solvent described in step (2)
0.01mg/mL~100mg/mL, such as 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 other unrequited numerical value are equally applicable in cited numerical value, the number range, preferably
It is 0.1mg/mL~10mg/mL.
Used as currently preferred technical scheme, 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, methyl alcohol, ethanol, isopropanol,
In n-hexane, normal heptane, normal octane or petroleum ether any one 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 methyl alcohol, ethanol 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, methyl alcohol, ethanol, isopropanol and n-hexane, ethanol, isopropanol, n-hexane, normal heptane, just
Combination of octane and petroleum ether etc..
Preferably, the addition of precipitating reagent is described in step (3)：The precipitating reagent disperses with the two-dimensional material just
The volume ratio of the dispersion liquid in solvent is 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 number range, other are not
The numerical value enumerated is equally applicable, and preferably 1:(0.5~10).
Preferably, the rotating speed of centrifugation 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 number range, other are not
The numerical value enumerated is equally applicable, preferably 1000r/min~6000r/min.
Preferably, the centrifugation time of centrifugation 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 other unrequited numerical value in cited numerical value, the number range equally applicable, preferably 5min~60min.
Preferably, the aperture of filter membrane used or filter paper is 1 μm~100 μm, such as 1 μm, 5 μ in being filtered described in step (3)
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
Other unrequited numerical value are equally applicable in numerical value, the number range.
Preferably, described in step (3) dry for vacuum drying, heat up dry or freeze-drying in any one or at least
Two kinds of combination, the combination is typical but non-limiting examples have：Be vacuum dried and heat up dry combination, heats up and dries and cold
Freeze dry combination, vacuum drying, intensification are dried and frozen dry combination etc..
Second aspect, the invention provides the preparation method of two-dimensional material powder dispersion, methods described is：
The two-dimensional material powder that above-mentioned preparation method is prepared is added in redisperse agent, is then sonicated, and is obtained
To dispersion liquid of the two-dimensional material in redisperse agent.
There is preferable pervasive performance by two-dimensional material obtained in the method for the invention, can be scattered in again various molten
In agent, and remain in that preferable performance.
Used as currently preferred technical scheme, the redisperse solvent is water, methyl alcohol, ethanol, isopropanol, acetone, fourth
Ketone, 1-METHYLPYRROLIDONE, NVP, N- cyclohexyl pyrrolidones, NOP, N- dodecyls
Pyrrolidones, gamma-butyrolacton, formamide, N-METHYLFORMAMIDE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, diformazan
In base sulfoxide, benzene, chlorobenzene, bromobenzene, benzonitrile, benzaldehyde, Ergol or benzyl ether any one or at least two group
Close, the combination is typical but non-limiting examples have：The combination of water and methyl alcohol, the combination of ethanol, isopropanol and acetone, butanone,
The combination of 1-METHYLPYRROLIDONE and NVP, NVP, N- cyclohexyl pyrrolidones and N-
The combination of octylpyrrolidone, the combination of N-dodecylpyrrolidone, gamma-butyrolacton and formamide, N, N- dimethylacetamide
The combination of amine, dimethyl sulfoxide (DMSO) and benzene, the combination of benzene, chlorobenzene, bromobenzene and benzonitrile, benzaldehyde, Ergol and benzyl ether
Combination, the combination of methyl alcohol, ethanol, isopropanol, acetone and butanone, 1-METHYLPYRROLIDONE, NVP, N- rings
The combination of hexyl pyrrolidones, NOP and N-dodecylpyrrolidone, gamma-butyrolacton, formamide, N- methyl
The combination dimethyl sulfoxide (DMSO) of formamide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and dimethyl sulfoxide (DMSO), benzene, chlorobenzene,
Combination of bromobenzene, benzonitrile, benzaldehyde, Ergol and 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 number range
Other unrequited 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
In the range of other unrequited numerical value it is equally applicable, preferably 1h~50h.
Preferably, in dispersion liquid of the two-dimensional material in redisperse agent two-dimensional material concentration for 0.01mg/mL~
100mg/mL, such as 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 other unrequited numerical value are equally applicable in cited numerical value, the number range, preferably 0.1mg/mL
~10mg/mL.
The two-dimensional material prepared by the method for the invention can keep preferably dividing in various redisperse agent
Performance is dissipated, the concentration of the dispersion liquid for obtaining is also higher.
Preferably, the size of two-dimensional material is 1nm~5000nm in dispersion liquid of the two-dimensional material in redisperse agent,
Such as 1nm, 10nm, 100nm, 500nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000nm, 3500nm, 4000nm,
4500nm or 5000nm etc., it is not limited to other unrequited numerical value are equally fitted in cited numerical value, the number range
With, preferably 1nm~500nm,.
Preferably, in dispersion liquid of the two-dimensional material in redisperse agent two-dimensional material thickness for 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
In the range of other unrequited numerical value it is equally applicable.
Compared with prior art, the invention has the advantages that：
(1) the method for the invention is obtained two-dimensional material powder by way of ball grinding method, ultrasonically treated combination are precipitated,
It is more easy compared with prior art, and overcoming cannot less than the two-dimensional material of filter membrane for size present in existing filter method
Play the problem for efficiently separating；Meanwhile, in also overcoming existing filter method the duration is long, it is impossible to which large-scale production is asked
Topic；
(2) dispersion that two-dimensional material powder obtained in the method for the invention can be good in multi-solvents, overcomes
Powder cannot effectively be dispersed to the problem in multi-solvents in the prior art, make obtained two-dimensional material powder in different solvents
Scattered concentration reaches as high as 100mg/mL.
Brief description of the drawings
Fig. 1 is raw materials used MoS in embodiment of the present invention 1-52Scanning electron microscope (SEM) photograph；
Fig. 2 is obtained MoS in the embodiment of the present invention 12The outward appearance photo of two-dimensional material powder；
Fig. 3 is obtained MoS in embodiment of the present invention 1-52Dispersion liquid of the two-dimensional material powder in different redisperse agent
Outward appearance photo；
Fig. 4 is obtained MoS 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 obtained WS in the embodiment of the present invention 62The outward appearance photo of two-dimensional material powder；
Fig. 7 is obtained WS in the embodiment of the present invention 62The outward appearance of two-dimensional material powder N,N-dimethylformamide dispersion liquid
Photo；
Fig. 8 is obtained WS 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
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only simple example of the invention, the scope of the present invention is not represented or limits, this
Invention protection domain is defined by claims.
Specific embodiment of the invention part provides two-dimensional material raw powder's production technology, and methods described includes following step
Suddenly：
(1) two-dimensional material raw material is carried out into ball milling, obtains solid material；
(2) to just dispersion solvent is added in gained solid material in step (1), carry out just ultrasonically treated, obtain two-dimentional material
Expect the dispersion liquid in first dispersion solvent；
(3) to precipitating reagent is added in dispersion liquid of the two-dimensional material in first dispersion solvent described in step (2), precipitation 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 obtained in the above method
Method, methods described is：
By in the addition redisperse agent of above-mentioned two-dimensional material powder, it is then sonicated, is obtained two-dimensional material in redisperse
Dispersion liquid in agent.
It is below present invention typical case but non-limiting example：
Embodiment 1：
Present embodiments provide a kind of MoS2Two-dimensional material raw powder's production technology, the described method comprises the following steps：
(1) by raw material MoS that 1g average-sizes are 5 μm2(its ESEM is as shown in Figure 1), 2g grinding aids sodium chloride and
Then the agate ball mixing of a diameter of 0.5mm of 10g, ball milling 0.5h separates agate ball, and gained samples with water is cleaned multiple times, directly
To washing sodium chloride completely to the greatest extent, vacuum drying obtains solid material；
(2) to first dispersion solvents 1-METHYLPYRROLIDONE (NMP) of addition 1L in gained solid material in step (1), with
The ultrasonic power ultrasound 12h of 100W, obtains MoS2Dispersion liquid in first dispersion solvent；
(3) to MoS in step (2)21L precipitating reagent ethyl acetate is added in dispersion liquid in first dispersion solvent, treats that it fills
After fractional precipitation, with the rotating speed centrifugation 10min of 2000r/min, sediment fraction is vacuum dried, obtains MoS2Two-dimensional material powder
Body.
The present embodiment additionally provides above-mentioned MoS2The preparation method of two-dimensional material powder aqueous dispersions, methods described is as follows：
By the above-mentioned MoS of 0.1g2Two-dimensional material powder is added in 5mL redisperse agent water, with the power ultrasonic 5h of 200W, is obtained
MoS2Two-dimensional material powder aqueous dispersions, its outward appearance photo is as shown in Figure 3.
Obtained MoS2Two-dimensional material powder aqueous dispersions dilute the uv-visible absorption spectra such as Fig. 4 institutes after 500 times
Show, calculated using Lambert-Beer law knowable to, 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, methods described is such as
Under：
By the above-mentioned MoS of 0.1g2Two-dimensional material powder is added in 5mL redisperse agent ethanol, with the power ultrasonic 5h of 200W, is obtained
To MoS2Two-dimensional material powder alcohol dispersion liquid, its outward appearance photo is 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, methods described 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 ultrasonic 5h of 200W, is obtained
To MoS2Two-dimensional material powder acetone dispersion liquor, its outward appearance photo is 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 DMF dispersion liquid,
Methods described is as follows：
By the above-mentioned MoS of 0.1g2Two-dimensional material powder is added in 5mL redisperse agent DMFs, with 200W's
Power ultrasonic 5h, obtains MoS2Two-dimensional material powder DMF dispersion liquid, its outward appearance photo is 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 liquids, methods described is as follows：
By the above-mentioned MoS of 0.1g2Two-dimensional material powder is added in 5mL redisperse agent NMP, with the power ultrasonic 5h of 200W, is obtained
To MoS2The concentration of two-dimensional material powder is the MoS of 20mg/mL2Two-dimensional material powder NMP dispersion liquids, its outward appearance photo such as Fig. 3 institutes
Show.
Be 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 is 5 μm.Obtained MoS2The outward 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 obtained in embodiment 1-52The water of two-dimensional material powder, ethanol, acetone, N,N-dimethylformamide and NMP point
The outward 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) by raw material WS that 1g average-sizes are 2 μm2(its ESEM is as shown in Figure 5), 1g grinding aids sodium carbonate and
Then the stainless steel ball mixing of a diameter of 20mm of 100g, ball milling 120h separates stainless steel ball, and gained samples with water is repeatedly clear
Wash, until sodium carbonate is washed completely to the greatest extent, vacuum drying obtains solid material；
(2) to first dispersion solvents 1-METHYLPYRROLIDONE (NMP) of addition 10mL in gained solid material in step (1), with
The ultrasonic power ultrasound 0.5h of 1000W, obtains WS2Dispersion liquid in first dispersion solvent；
(3) to WS in step (2)240mL precipitating reagent Ethyl formates are added in dispersion liquid in first dispersion solvent, it is treated
Fully after precipitation, with the rotating speed centrifugation 40min of 5000r/min, sediment fraction is vacuum dried, obtains WS2Two-dimensional material
Powder.
The present embodiment additionally provides above-mentioned WS2The preparation method of two-dimensional material powder DMF dispersion liquids, methods described is as follows：
By the above-mentioned MoS of 0.05g2Two-dimensional material powder is added in 50mL redisperse agent DMF (DMF), with
The power ultrasonic 1h of 1000W, obtains WS2Two-dimensional material powder DMF dispersion liquids, its outward appearance photo is as shown in Figure 7.
Fig. 5 is WS in embodiment 62The stereoscan photograph of raw material, it is seen that its size is 1 μm~10 μm, and average-size is 2
μm.Fig. 6 is the WS prepared by embodiment 62The outward appearance photo of two-dimensional material powder, it is black, in the form of sheets, and with glossy.
Fig. 7 is the WS prepared by embodiment 62Two-dimensional material DMF dispersion liquid outward appearance photos, WS2Two-dimensional material DMF dispersion liquids are in kermesinus.
Fig. 7 is the WS prepared by embodiment 62Two-dimensional material aqueous dispersions dilute the uv-visible absorption spectra after 20 times, using blue primary
Knowable to spy-Beer law is calculated, 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, be the described method comprises the following steps：
(1) by raw graphite, 0.1g grinding aids calcium carbonate and a diameter of 6mm of 10g that 0.01g average-sizes are 100 μm
Zirconia balls mix, and then ball milling 20h separate zirconia balls, and 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, and remaining hydrochloric acid is washed to the greatest extent completely, and vacuum drying obtains solid material；
(2) to 1mL just dispersion solvents dimethyl sulfoxide (DMSO) (DMSO) are added in gained solid material in step (1), with 200W
Ultrasonic power ultrasound 5h, obtain dispersion liquid of the graphite in first dispersion solvent；
(3) to 100mL precipitating reagent ethyl acetate is added in dispersion liquid of the graphite in first dispersion solvent in step (2), treat
After it is fully precipitated, with the rotating speed centrifugation 20min of 10000r/min, sediment fraction is vacuum dried, 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 methods described is such as
Under：
During the above-mentioned graphite two-dimensional material powders of 0.005g are added into 5mL redisperse agent acetone, with the power ultrasonic of 300W
12h, obtains graphite two-dimensional material powder acetone dispersion liquor, and its concentration is 100mg/mL.
Embodiment 8：
A kind of h-BN two-dimensional materials raw powder's production technology is present embodiments provided, be the described method comprises the following steps：
(1) by the nitridation of raw material h-BN, 10g grinding aid ammonium chloride and a diameter of 3mm of 50g that 1g average-sizes are 0.1 μm
Silicon ball mixes, and then ball milling 10h separates silicon nitride ball, and gained samples with water is cleaned multiple times, until ammonium chloride is washed completely
To the greatest extent, vacuum drying, obtains solid material；
(2) to 50mL just dispersion solvent DMFs are added in gained solid material in step (1), with 400W
Ultrasonic power ultrasound 3h, obtain dispersion liquids of the h-BN in first dispersion solvent；
(3) to 100mL precipitating reagent methyl formates are added in dispersion liquids of the h-BN in first dispersion solvent in step (2), treat
After it is fully precipitated, with the rotating speed centrifugation 30min of 5000r/min, sediment fraction is vacuum dried, obtains h-BN two dimension materials
Feed powder body.
The present embodiment additionally provides the preparation method of above-mentioned h-BN two-dimensional materials powder NMP dispersion liquids, and methods described is as follows：
During the above-mentioned h-BN two-dimensional materials powders of 0.3g are added into 50mL redisperse agent acetone, with the power ultrasonic 24h of 600W,
Obtain h-BN two-dimensional material powder NMP dispersion liquids.
Embodiment 9：
A kind of two selenizings molybdenum two-dimensional material raw powder's production technology is present embodiments provided, methods described includes following step
Suddenly：
(1) silicon nitride ball of the selenizing molybdenum of raw material two that 0.5g average-sizes are 0.2 μm and a diameter of 3mm of 30g is mixed, ball
Mill 10h, adds the hard tungsten-carbide ball mixing of 14mm, and then ball milling 7h separates ball milling ball, and vacuum drying obtains solid
Material；
(2) to 50mL just dispersion solvent N-METHYLFORMAMIDEs are added in gained 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) to addition 10mL precipitating reagent ethyl acetate in dispersion liquid of the two selenizing molybdenums in first dispersion solvent in step (2),
After it is fully precipitated, with the rotating speed centrifugation 60min of 2500r/min, sediment fraction is vacuum dried, obtains two selenizing molybdenums
Two-dimensional material powder.
The present embodiment additionally provides the preparation method of above-mentioned two selenizings molybdenum two-dimensional material powder DMSO dispersion liquids, methods described
It is as follows：
During the above-mentioned two selenizings molybdenum two-dimensional material powders of 0.2g are added into 10mL redisperse agent acetone, with the power ultrasonic 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 is precipitated by ball grinding method, ultrasonically treated combination
Formula is obtained two-dimensional material powder, and it is more easy compared with prior art, overcomes small for size present in existing filter method
The problem for efficiently separating cannot be played in the two-dimensional material of filter membrane；Meanwhile, the duration is long in also overcoming existing filter method,
The problem that cannot be mass produced.
Also, two-dimensional material powder obtained in the method for the invention can be good in multi-solvents dispersion, overcome
Powder cannot effectively be dispersed to the problem in multi-solvents in the prior art, make obtained two-dimensional material powder in different solvents
In scattered concentration reach as high as 100mg/mL.
Applicant states that the present invention illustrates detailed process equipment of the invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, the selection of concrete mode to the equivalence replacement and auxiliary element of each raw material of product of the present invention etc., all fall within of the invention
Within the scope of protection domain and disclosure.
Claims (8)
1. two-dimensional material raw powder's production technology, it is characterised in that the described method comprises the following steps：
(1) two-dimensional material raw material is carried out into ball milling, obtains solid material；
(2) to just dispersion solvent is added in gained solid material in step (1), carry out just ultrasonically treated, obtain two-dimensional material and exist
Dispersion liquid in first dispersion solvent；
(3) to precipitating reagent is added in dispersion liquid of the two-dimensional material in first dispersion solvent described in step (2), precipitation is completely laggard
Row centrifugation or filtering, two-dimensional material powder is obtained after drying.
2. preparation method according to claim 1, it is characterised in that step (1) the two-dimensional material raw material is graphite, six
In square boron nitride, molybdenum bisuphide, tungsten disulfide, two selenizing molybdenums or two tungsten selenides any one or at least two combination；
Preferably, the size of step (1) the two-dimensional material raw material is 0.1 μm~100 μm, preferably 0.5 μm~10 μm.
3. preparation method according to claim 1 and 2, it is characterised in that step (1) is described to carry out two-dimensional material raw material
The specific method of ball milling is comprised the following steps：
A () mixes two-dimensional material raw material and ball milling ball, carry out ball milling；
B () is vacuum dried after the solid material after ball milling in step (a) is separated with ball milling ball, obtain 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, to being added in the material after separation, washing is molten
Agent, washing, vacuum drying obtains solid material.
4. preparation method according to claim 3, it is characterised in that ball milling ball described in step (a) and 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；
Preferably, step (a) and the diameter of ball milling ball described in step (a ') are independently 0.5mm~20mm；
Preferably, the time of ball milling described in step (a) and step (a ') is independently 0.5h~120h, and preferably 1h~
50h；
Preferably, step (a) and the addition of ball milling ball described in step (a ') are independently the two-dimensional material raw material matter
1 times~1000 times, preferably 50 times~300 times of amount；
Preferably, the addition of grinding aid described in step (a ') is 0 times~100 times of the two-dimensional material material quality and not
Including 0 times, preferably 1 times~30 times；
Preferably, by anion and cation composition, its cationic is the sun of IA races element to grinding aid described in step (a ')
In ion, the cation of Group IIA element or ammonium root cation any one or at least two combination, anion be hydroxyl from
Son, chlorion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate anion, phosphoric acid hydrogen radical ion, biphosphate
In radical ion, carbanion, bicarbonate ion or citrate ion any one or at least two combination；
Preferably, cleaning solvent described in step (b ') be water, hydrochloric acid, sulfuric acid or nitric acid in any one or at least two group
Close；
Preferably, washing is described in step (b ')：Grinding aid in solid material after the ball milling is washed completely；
Preferably, vacuum drying temperature described in step (b) and (b ') is independently 0 DEG C~100 DEG C, preferably 20 DEG C~
60℃。
5. the preparation method according to claim any one of 1-4, it is characterised in that first dispersion solvent described in step (2)
It is 1-METHYLPYRROLIDONE, NVP, N- cyclohexyl pyrrolidones, NOP, N- dodecyls
Pyrrolidones, gamma-butyrolacton, formamide, N-METHYLFORMAMIDE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or two
In methyl sulfoxide any one or at least two combination；
Preferably, described in step (2) just it is ultrasonically treated in Vltrasonic device for probe type Vltrasonic device and/or water-bath type ultrasound
Device；
Preferably, ultrasonic power just ultrasonically treated described in step (2) is 50W~1000W, preferably 100W~500W；
Preferably, ultrasonic time just ultrasonically treated described in step (2) is 0.5h~120h, preferably 1h~50h；
Preferably, the concentration of two-dimensional material is in dispersion liquid of the two-dimensional material in first dispersion solvent described in step (2)
0.01mg/mL~100mg/mL, preferably 0.1mg/mL~10mg/mL.
6. the preparation method according to claim any one of 1-5, it is characterised in that precipitating reagent described in step (3) is first
Sour methyl esters, Ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propionic acid third
In ester, methyl alcohol, ethanol, isopropanol, n-hexane, normal heptane, normal octane or petroleum ether any one or at least two combination；
Preferably, the addition of precipitating reagent is described in step (3)：The precipitating reagent is with the two-dimensional material in first dispersion solvent
In dispersion liquid volume ratio be 1:(0.01~100), preferably 1:(0.5~10)；
Preferably, the rotating speed of centrifugation described in step (3) is 500r/min~10000r/min, preferably 1000r/min
~6000r/min；
Preferably, the centrifugation time of centrifugation described in step (3) is 1min~120min, preferably 5min~60min；
Preferably, the aperture of filter membrane used or filter paper is 1 μm~100 μm in being filtered described in step (3)；
Preferably, described in step (3) dry for vacuum drying, heat up dry or freeze-drying in any one or at least two
Combination.
7. the preparation method of two-dimensional material powder dispersion, it is characterised in that methods described is：
The two-dimensional material powder that claim any one of 1-6 is prepared is added in redisperse agent, is then sonicated, and is obtained
To dispersion liquid of the two-dimensional material in redisperse agent.
8. preparation method according to claim 7, it is characterised in that the redisperse solvent is water, methyl alcohol, ethanol, different
Propyl alcohol, acetone, butanone, 1-METHYLPYRROLIDONE, NVP, N- cyclohexyl pyrrolidones, N- octyl group pyrrolidines
Ketone, N-dodecylpyrrolidone, gamma-butyrolacton, formamide, N-METHYLFORMAMIDE, N,N-dimethylformamide, N, N- diformazans
In yl acetamide, dimethyl sulfoxide (DMSO), benzene, chlorobenzene, bromobenzene, benzonitrile, benzaldehyde, Ergol or benzyl ether any one or
At least two combination；
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 is 50W~1000W, preferably 100W~500W；
Preferably, the ultrasonic time being then sonicated is 0.5h~120h, preferably 1h~50h；
Preferably, in dispersion liquid of the two-dimensional material in redisperse agent two-dimensional material concentration for 0.01mg/mL~
100mg/mL, preferably 0.1mg/mL~10mg/mL.
Preferably, the size of two-dimensional material is 1nm~5000nm in dispersion liquid of the two-dimensional material in redisperse agent, preferably
It is 1nm~500nm；
Preferably, the thickness of two-dimensional material is 1 layer~10 layers in dispersion liquid of the two-dimensional material in redisperse agent.
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