CN109817382A - A kind of preparation method of high-stability graphene electrocondution slurry - Google Patents
A kind of preparation method of high-stability graphene electrocondution slurry Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of graphene conductive slurry, include the following steps, after first being removed graphite dispersing solution under conditions of ultrasound, then separate, obtain graphene nanometer sheet；Then after being mixed graphene nanometer sheet, dispersing agent and solvent that above-mentioned steps obtain, pre- slurry is obtained；After the pre- slurry that finally above-mentioned steps are obtained carries out homogeneous mashing, graphene conductive slurry is obtained.The present invention has selected the liquid phase stripping method of low-temperature atmosphere-pressure, using graphite-solvent mixing-high-pressure homogeneous method of ultrasonic disperse-, first prepare graphene nanometer sheet, then prepare stable graphene conductive slurry again, can in a mild condition quickly, prepare graphene at low cost.And graphene prepared by the present invention has complete lamellar structure, it is not surface modified, the intrinsic feature for keeping two-dimensional slice, has the characteristics that high conductivity, high stability, can be used as conductive additive in fields such as lithium battery, supercapacitor, conductive coatings.
Description
Technical field
The invention belongs to technical field of graphene, are related to a kind of preparation method more particularly to one of graphene conductive slurry
The preparation method of kind high-stability graphene electrocondution slurry.
Background technique
Graphene be as six side of single layer of carbon atom it is tightly packed made of two dimensional crystal material, thickness is about 0.335 nanometer,
With perfect crystal structure, electric conductivity with super strength is the best material of current electric conductivity, theoretical electronic transfer rate
For 200000cm2/V.S, theoretical thermal conductivity is 5000W/m.K.Graphene because its conductive, superelevation specific surface area, solely
The excellent performances such as special two-dimensional network structure, high intensity and high electron mobility, cause the extensive concern of people, Jin Erye
Promote the fast development of graphene preparation technology.Just because of with above-mentioned many excellent physical chemical property, storing up
Energy material, environmental project, sensing sensitive aspect are widely used, referred to as " dark fund " or " king of new material ", and potential
Application prospect it is vast, have become global focus and research hotspot at present.
For the such application for realizing graphene, can prepare the preparation method with excellent properties graphene just becomes necessary
Task.However in practical applications, the preparation of graphene is exactly a main barrier for restricting graphene practical application and development
Hinder.Although scientific research personnel has developed numerous graphene preparation methods so far.The method for wherein comparing mainstream has graphite oxide
Reduction method, epitaxial growth method and chemical vapour deposition technique (CVD) etc..Graphite oxide reduction method is prepare graphene at present best
One of method is to react natural graphite with strong acid and oxidizing species to generate graphite oxide, is prepared by ultrasonic disperse
Graphene oxide (mono-layer graphite oxide), be added reducing agent removal graphite oxide surface oxygen-containing group, as carboxyl, epoxy group and
Hydroxyl obtains graphene.This method is easy to operate, preparation cost is low, can prepare graphene on a large scale, but because it is being made
The strong oxidizer concentrated sulfuric acid or potassium permanganate etc. are introduced during standby, inevitably destroys the lattice structure of graphene, are introduced
A large amount of defects, so as to cause the serious loss of graphene intrinsic performance.
Chemical vapour deposition technique (Chemical Vapor Deposition, CVD) refers to reactive material under gaseous condition
It chemically reacts, generates the solid matrix surface that solid matter is deposited on heating, and then the technology of solid material is made.
Although the graphite of the high-quality large area of complete, the few defect of lattice can be obtained with epitaxial growth method and chemical vapour deposition technique
Alkene, but its preparation cost valuableness, low yield, preparation process require harshness, are unable to satisfy the business needs of large-scale production.Thus
Above-mentioned these preparation methods are not met by the requirement of high-quality graphene industrialization in reality.
Solvent stripping method is just to propose for nearest 2 years, its principle is formed by a small amount of graphite dispersion in solvent
The dispersion liquid of low concentration carries out intercalation at high temperature under high pressure, destroys the Van der Waals force of graphite layers, and solvent can be inserted at this time
Enter graphite layers, removed layer by layer, prepares graphene.The method will not destroy graphene as oxidation-reduction method
Structure can prepare the graphene of high quality.But there are the high requirements on the equipment, react the problems such as dangerous and at high cost, and
The problem of there is also chemical reagent pollutions.
More important is no matter the graphene of which kind of above-mentioned method preparation is short of stability, and it is easy can not to solve graphene
The inherent shortcoming of reunion, so that graphene deficient in stability in application.
Therefore, in order to preferably realize the business application of graphene, a kind of more environmentally friendly preparation high-quality stone how is obtained
The method of black alkene, while the defect for overcoming graphene easy to reunite, improve its stability, are that each R & D Enterprises are faced in field
One of key challenges and urgent problem to be solved.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of preparation method of graphene conductive slurry,
Especially a kind of low temperature preparation method of high-stability graphene electrocondution slurry, room temperature liquid phase stripping method provided by the invention, energy
The graphene for obtaining having better electric conductivity quickly, inexpensive in a mild condition, and compounding aid are formed high steady
Qualitative graphene conductive slurry, can be used as conductive additive in fields such as lithium battery, supercapacitors.
The present invention provides a kind of preparation methods of graphene conductive slurry, comprising the following steps:
1) it after being removed graphite dispersing solution under conditions of ultrasound, then separates, obtains graphene nanometer sheet；
2) after being mixed graphene nanometer sheet, dispersing agent and solvent that above-mentioned steps obtain, pre- slurry is obtained；
3) after the pre- slurry for obtaining above-mentioned steps carries out homogeneous mashing, graphene conductive slurry is obtained.
Preferably, the graphite in the graphite dispersing solution includes graphite powder, crystalline flake graphite, artificial graphite, expansible graphite
With one of expanded graphite or a variety of；
The mass concentration of graphite is 0.5%~5% in the graphite dispersing solution；
Solvent in the graphite dispersing solution includes water and organic solvent miscible with water.
Preferably, the organic solvent miscible with water include methanol, ethyl alcohol, ethylene glycol, glycerol, acetone, tetrahydrofuran,
One of dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone and dimethyl sulfoxide are a variety of；
Mass concentration of the organic solvent miscible with water in the graphite dispersing solution is 30%~70%；
The power of the ultrasound is 600~3000W；The time of the ultrasound is 1~20h；
It further include drying steps after the separation.
Preferably, the mode of the removing includes one of stirring, shearing, ball milling and sand milling or a variety of；
The phosphorus content of the graphene nanometer sheet is more than or equal to 98%；
The graphene nanometer sheet with a thickness of be less than or equal to 5nm；
The piece diameter of the graphene nanometer sheet is 1~20 μm.
Preferably, the dispersing agent includes polyvinylpyrrolidone, Vingon, polypropylene, cetyl trimethyl
One of ammonium bromide and neopelex are a variety of；
The solvent includes water, ethyl alcohol, acetone, dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone and two
One of methyl sulfoxide is a variety of；
In the pre- slurry, the mass concentration of the dispersing agent is 0.2%~10%；
In the pre- slurry, the mass concentration of the graphene nanometer sheet is 1%~10%.
Preferably, the homogeneous is super-high-pressure homogenization；
The number of the homogeneous is 1~20 time；
The conductivity of the graphene conductive slurry is more than or equal to 40000S/m.
Preferably, the pressure of the super-high-pressure homogenization is 400~1500bar；
The processing speed of the super-high-pressure homogenization is 5~15L/h.
Preferably, the graphite is to pass through pretreated graphite；
The pretreated step are as follows:
A after) being reacted graphite and small molecule intercalator, intercalated graphite is obtained；
B) intercalated graphite for obtaining above-mentioned steps is after high-temperature expansion, the graphite that obtains that treated.
Preferably, the granularity of the graphite is 50~10000 mesh；
The carbon content of the graphite is more than or equal to 70%；
The small molecule intercalator includes small molecule high temperature decomposable compound；
The time of the reaction is 10~30 hours；The temperature of the reaction is 0~40 DEG C.
Preferably, the small molecule intercalator includes sulfuric acid, nitric acid, urea, sodium bicarbonate, carbonic acid sodium dihydrogen, bicarbonate
One of disodium, oxalic acid, phosphoric acid, perchloric acid, periodic acid and trifluoromethanesulfonic acid are a variety of；
The mass ratio of the graphite and small molecule intercalator is 1:(1~5)；
The temperature of the high-temperature expansion is 500~1200 DEG C；
The time of the high-temperature expansion is 5~60 seconds.
The present invention provides a kind of preparation methods of graphene conductive slurry, include the following steps, first by graphite dispersion
It after liquid is removed under conditions of ultrasound, then separates, obtains graphene nanometer sheet；Then graphene above-mentioned steps obtained
After nanometer sheet, dispersing agent and solvent are mixed, pre- slurry is obtained；The pre- slurry that above-mentioned steps obtain finally is carried out homogeneous to beat
After slurry, graphene conductive slurry is obtained.Compared with prior art, the present invention can be prepared for existing micromechanics stripping method
High-quality graphene, but there are low yields and deficiency at high cost, are unsatisfactory for industrialization and large-scale production requirement, at present can only
It is prepared on a small scale as laboratory.Chemical vapour deposition technique can prepare the graphene of high quality large area, but ideal
The expensive of substrate material monocrystalline nickel, greatly limits graphene industrialized production, higher cost, complex process.Oxidation-
Reduction method will lead to the loss of graphene part electric property, be restricted the application of graphene.And conventional solvent removing
The problem of high temperature and pressure defect existing for method and low yield.The present invention has selected the liquid phase stripping method of low-temperature atmosphere-pressure, creative
Then prepared again using graphite-solvent mixing-high-pressure homogeneous method of ultrasonic disperse-by first preparing graphene nanometer sheet
Stable graphene conductive slurry, can in a mild condition quickly, prepare graphene at low cost.And it is prepared by the present invention
Graphene has complete lamellar structure, is not surface modified, keeps the intrinsic feature of two-dimensional slice.It is prepared by the present invention
Graphene conductive slurry has the characteristics that high conductivity, high stability, can be used as conductive additive in lithium battery, super capacitor
The fields such as device, conductive coating.
The experimental results showed that highly conductive graphene slurry prepared by the present invention, carbon content is more than or equal to 99.5%, conductivity
Greater than 50000S/m, 70000S/m can be reached, at a high temperature of 60 DEG C, storage 48h or more can be stablized.
Detailed description of the invention
Fig. 1 is the atomic force microscopy of highly conductive graphene prepared by the embodiment of the present invention 1；
Fig. 2 is that the thickness data that the highly conductive graphene of preparation of the embodiment of the present invention is measured by atomic force microscope is bent
Line；
Fig. 3 is the field emission scanning electron microscope photo of highly conductive graphene prepared by the embodiment of the present invention 1；
Fig. 4 is the high-resolution-ration transmission electric-lens photo of highly conductive graphene prepared by the embodiment of the present invention 1；
Fig. 5 is the field emission scanning electron microscope photo of highly conductive graphene prepared by the embodiment of the present invention 2；
Fig. 6 is the high-resolution-ration transmission electric-lens photo of highly conductive graphene prepared by the embodiment of the present invention 2；
Fig. 7 is the field emission scanning electron microscope photo of highly conductive graphene prepared by the embodiment of the present invention 3；
Fig. 8 is the high-resolution-ration transmission electric-lens photo of highly conductive graphene prepared by the embodiment of the present invention 3.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze the preparation of pure or graphene
The purity requirement of field routine.
All raw materials of the present invention, the trade mark and abbreviation belong to this field routine trade mark and abbreviation, each trade mark and abbreviation
In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes,
It can be commercially available from city's mid-sales or conventional method is prepared.
The present invention provides a kind of preparation methods of graphene conductive slurry, comprising the following steps:
1) it after being removed graphite dispersing solution under conditions of ultrasound, then separates, obtains graphene nanometer sheet；
2) after being mixed graphene nanometer sheet, dispersing agent and solvent that above-mentioned steps obtain, pre- slurry is obtained；
3) after the pre- slurry for obtaining above-mentioned steps carries out homogeneous mashing, graphene conductive slurry is obtained.
It after the present invention first removes graphite dispersing solution under conditions of ultrasound, then separates, obtains graphene nano
Piece.
The selection of graphite in the graphite dispersing solution is not particularly limited in the present invention, with well known to those skilled in the art
Graphite material, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, graphite of the present invention preferably include in graphite powder, crystalline flake graphite, artificial graphite, expansible graphite and expanded graphite
One or more, more preferably graphite powder, crystalline flake graphite, artificial graphite, expansible graphite or expanded graphite.
The granularity of graphite in the graphite dispersing solution is not particularly limited in the present invention, with well known to those skilled in the art
The partial size of graphite powder, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, graphite dispersing solution of the present invention are preferably the dispersion liquid of graphite powder, and the granularity of the graphite is preferably 50~
10000 mesh, more preferably 100~5000 mesh, more preferably 500~3000 mesh, most preferably 1000~2000 mesh.
The carbon content of graphite in the graphite dispersing solution is not particularly limited in the present invention, known to those skilled in the art
Graphite powder carbon content, those skilled in the art can be according to practical condition, product requirement and quality requirement
It is selected and is adjusted, the carbon content of graphite of the present invention is preferably greater than or equal to 70%, optimal more preferably greater than equal to 80%
It is selected as being more than or equal to 90%, is specifically as follows 70%~95%, or 75%~90%, or be 78%~93%.
The concentration of graphite in the graphite dispersing solution is not particularly limited in the present invention, with well known to those skilled in the art
Normal concentration, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the present invention are to improve the performance of subsequent product, improve the uniformity of graphite dispersing solution, graphite dispersing solution of the present invention
The mass concentration of middle graphite is preferably 0.5%~5%, and more preferably 1.5%~4%, more preferably 2.5%~3%.
The solvent in the graphite dispersing solution is not particularly limited in the present invention, with routine well known to those skilled in the art
Solvent, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, the present invention is to improve the performance of subsequent product, improves the uniformity of graphite dispersing solution, and the solvent in the graphite dispersing solution is special
Water and organic solvent miscible with water are not preferably included.Organic solvent miscible with water of the present invention preferably includes methanol, second
Alcohol, ethylene glycol, glycerol, acetone, tetrahydrofuran, dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone and dimethyl
One of sulfoxide is a variety of, more preferably methanol, ethyl alcohol, ethylene glycol, glycerol, acetone, tetrahydrofuran, dimethylformamide,
Dimethyl acetamide, N-Methyl pyrrolidone or dimethyl sulfoxide.
The concrete composition ratio of the solvent in the graphite dispersing solution is not particularly limited in the present invention, with art technology
Conventional proportions known to personnel, those skilled in the art can want according to practical condition, product requirement and quality
It asks and is selected and adjusted, the present invention is to improve the performance of subsequent product, improves the uniformity of graphite dispersing solution, described mutual with water
Mass concentration of the molten organic solvent in the graphite dispersing solution is preferably 30%~70%, and more preferably 40%~60%,
More preferably 45%~55%.
The mode of the removing is not particularly limited in the present invention, with the side of such removing well known to those skilled in the art
Formula, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
The present invention is to improve the performance of final products, and the mode of the removing is preferably mechanical stripping, i.e., using mechanical stripping and ultrasound
The mode of collocation is removed, and is specifically preferably included one of stirring, shearing, ball milling and sand milling or a variety of, is more preferably stirred
It mixes, shear, ball milling and sand milling, and carrying out ultrasound simultaneously.
The temperature of the removing is not particularly limited in the present invention, with the temperature of such removing well known to those skilled in the art
Degree, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
The present invention is to improve the advantage of the performance and liquid phase separation method of final products, and the temperature of the removing is preferably room temperature, i.e., preferably
It is 0~40 DEG C, more preferably 5~35 DEG C, more preferably 10~30 DEG C, more preferably 15~25 DEG C.
The condition of the ultrasound is not particularly limited in the present invention, is with normal condition well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright performance to improve subsequent product, improves the uniformity of graphite dispersing solution, and the power of the ultrasound is preferably 600~3000W,
More preferably 1100~2500W, more preferably 1600~2000W.The time of the ultrasound, that is, the time removed, preferably 1~
20h, more preferably 5~16h, more preferably 9~12h, are specifically as follows 1h, 2h, 8h or 20h.
The isolated mode is not particularly limited in the present invention, with conventional separate mode well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
It invents the separation to be preferably separated by filtration, more specifically preferably includes to filter.It is also preferable to include dryings after separation of the present invention
Step.The concrete mode and condition of the drying is not particularly limited in the present invention, with routine well known to those skilled in the art
Drying mode and condition, those skilled in the art can according to practical condition, product requirement and quality requirement into
Row selection and adjustment.
The present invention is the electric conductivity for further increasing subsequent product, improves the uniformity of graphite dispersing solution, the graphite
Graphite in dispersion liquid more preferably passes through pretreated graphite.The pretreated step specifically preferred according to the invention is specific
Are as follows:
A after) being reacted graphite and small molecule intercalator, intercalated graphite is obtained；
B) intercalated graphite for obtaining above-mentioned steps is after high-temperature expansion, the graphite that obtains that treated.
Selection and requirement and corresponding optimum principle of the present invention to graphite in above-mentioned steps, lead with foregoing graphites alkene
The selection and requirement of corresponding raw material in the preparation method of plasma-based material, and corresponding optimum principle can be corresponded to, herein
No longer repeat one by one.
After the present invention first reacts graphite and small molecule intercalator, intercalated graphite is obtained.
The selection of the small molecule intercalator is not particularly limited in the present invention, with small point well known to those skilled in the art
Sub- intercalator, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the present invention are to improve the performance of final products, the small molecule intercalator is preferably that small molecule high temperature can decompose chemical combination
Object, more preferably include sulfuric acid, nitric acid, urea, sodium bicarbonate, carbonic acid sodium dihydrogen, disodium bicarbonate, oxalic acid, phosphoric acid, perchloric acid,
One of periodic acid and trifluoromethanesulfonic acid are a variety of, more preferably sulfuric acid, nitric acid, urea, sodium bicarbonate, carbonic acid sodium dihydrogen,
Disodium bicarbonate, oxalic acid, phosphoric acid, perchloric acid, periodic acid or trifluoromethanesulfonic acid.More preferably sulfuric acid, nitric acid, urea, bicarbonate
Sodium, carbonic acid sodium dihydrogen, disodium bicarbonate, oxalic acid or phosphoric acid.
The dosage of the small molecule intercalator is not particularly limited in the present invention, and those skilled in the art can be according to reality
The condition of production, product requirement and quality requirement are selected and are adjusted, and the present invention is to improve the performance of final products, the stone
Ink and the mass ratio of small molecule intercalator are preferably 1:(1~5), more preferably 1:(1.5~4.5), more preferably 1:(2~4),
Most preferably 1:(2.5~3.5).
The temperature of the reaction is not particularly limited in the present invention, and those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted, and the present invention is to improve the performance and liquid phase separation method of final products
Advantage, reaction temperature is particularly maintained into room temperature, i.e., the temperature of the described reaction is preferably 0~40 DEG C, more preferably 5~35
DEG C, more preferably 10~30 DEG C, more preferably 15~25 DEG C.
The time of the reaction is not particularly limited in the present invention, with liquid phase separation method well known to those skilled in the art
Conventional intercalation time, those skilled in the art can be according to practical condition, product requirement and quality requirements
It being selected and is adjusted, the time of reaction of the present invention is preferably 10~30h, more preferably 12~28h, more preferably 15~
25h, more preferably 17~for 24 hours, it is specifically as follows 10h, 15h, 20h or 30h.
The present invention can decompose intercalator using small molecule high temperature and carry out intercalation, small molecule high temperature decomposable compound to graphite
It can be realized small molecule and enter interlayer, reduce graphite reaction, keep the complete structure of graphite flake layer；And also avoid high temperature height
The reaction condition of pressure has further lowered the temperature of intercalation, can be mild under the conditions of lower temperature and common room temperature etc.
Condition realizes effective intercalation of graphite, obtains graphite intercalation compound, reduces the loss and energy consumption of preparation process, green ring
It protects.
The present invention is to improve the practicability of preparation method, and complete process route, it is also preferable to include post-processings after the reaction
Step.The specific steps of the post-processing are not particularly limited in the present invention, with post-processing well known to those skilled in the art step
Rapid, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
Post-processing of the present invention is preferably included to wash and be separated, more specific to be preferably washed to neutral and centrifuge separation.
Then intercalated graphite that the present invention obtains above-mentioned steps obtains expanded graphite after high-temperature expansion.
The temperature of the high-temperature expansion is not particularly limited in the present invention, with such expansion well known to those skilled in the art
Temperature, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the present invention are to improve the advantage of the performance and liquid phase separation method of final products, and the temperature of the high-temperature expansion is preferably 500
~1200 DEG C, more preferably 600~1100 DEG C, more preferably 700~1000 DEG C, more preferably 800~900 DEG C.
The time of the high-temperature expansion is not particularly limited in the present invention, with high-temperature expansion well known to those skilled in the art
Time, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the time of high-temperature expansion of the present invention is preferably 5~60 seconds, more preferably 10~55 seconds, more preferably 15~50 seconds,
More preferably 25~40 seconds, it is specifically as follows 5 seconds, 10 seconds, 30 seconds or 60 seconds.
The present invention has obtained graphene nanometer sheet by above-mentioned steps.Specifics of the present invention to the graphene nanometer sheet
Energy parameter is not particularly limited, and the graphene nano of the specific performance can be obtained referring to the above method by those skilled in the art
Piece, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The phosphorus content of the bright graphene nanometer sheet is preferably greater than or equal to 98%, is more preferably greater than equal to 98.5%, more preferably greater than etc.
In 99%.The thickness of the graphene nanometer sheet, which is preferably less than, is equal to 5nm, is more preferably less than equal to 4nm, more preferably small
In equal to 3nm.The piece diameter of the graphene nanometer sheet is preferably 1~20 μm, more preferably 5~16 μm, more preferably 9~12 μ
m。
After the present invention then mixes graphene nanometer sheet, dispersing agent and solvent that above-mentioned steps obtain, obtain pre-
Slurry.
The specific choice of the dispersing agent is not particularly limited in the present invention, with routine well known to those skilled in the art point
Powder, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, the present invention is to improve the performance of subsequent product, improves the uniformity of pre- slurry, the dispersing agent preferably includes polyvinyl pyrrole
One of alkanone, Vingon, polypropylene, cetyl trimethylammonium bromide and neopelex are a variety of,
More preferably polyvinylpyrrolidone, Vingon, polypropylene, cetyl trimethylammonium bromide or dodecyl benzene sulfonic acid
Sodium.
The dosage of the dispersing agent is not particularly limited in the present invention, is with conventional amount used well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright performance to improve subsequent product, improves the uniformity of pre- slurry, and in the pre- slurry, the mass concentration of the dispersing agent is excellent
It is selected as 0.2%~10%, more preferably 0.7%~9%, more preferably 2%~8%, more preferably 4%~6%.
The specific choice of the solvent is not particularly limited in the present invention, with Conventional solvents well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
Invention is the performance for improving subsequent product, improves the uniformity of pre- slurry, the solvent preferably includes water, ethyl alcohol, acetone, diformazan
One of base formamide, dimethyl acetamide, N-Methyl pyrrolidone and dimethyl sulfoxide are a variety of, more preferably water, second
Alcohol, acetone, dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone or dimethyl sulfoxide.
The dosage of the solvent is not particularly limited in the present invention, with Conventional solvents dosage well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
Invention is the performance for improving subsequent product, improves the uniformity of pre- slurry, in the pre- slurry, the matter of the graphene nanometer sheet
Measuring concentration is preferably 1%~10%, and more preferably 2%~9%, more preferably 3%~8%, more preferably 4%~7%.
The mixed mode is not particularly limited in the present invention, is with hybrid mode well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright mixed mode is preferably stirred.
After the pre- slurry that the present invention finally obtains above-mentioned steps carries out homogeneous mashing, graphene conductive slurry is obtained.
The present invention is to improve the performance of final products, provides the stability and electric conductivity of graphene conductive slurry, especially
It is preferred that being beaten by the way of homogeneous.The concrete mode of the homogeneous is not particularly limited in the present invention, with this field skill
Homogeneous manner known to art personnel, those skilled in the art can be according to practical condition, product requirement and quality
It is required that being selected and being adjusted, the mode of homogeneous of the present invention is preferably super-high-pressure homogenization, i.e., using superhigh-voltage homogenizing machine into
Row homogeneous.The number of the homogeneous is not particularly limited in the present invention, with homogenization cycles well known to those skilled in the art,
Those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The number of the homogeneous is preferably 1~20 time, more preferably 5~16 times, more preferably 9~12 times.
The condition of the super-high-pressure homogenization is not particularly limited in the present invention, with super-pressure well known to those skilled in the art
Processing condition, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the pressure of super-high-pressure homogenization of the present invention are preferably 400~1500bar, more preferably 600~1300bar is more excellent
It is selected as 800~1100bar.The processing speed of the super-high-pressure homogenization is preferably 5~15L/h, more preferably 7~13L/h, more excellent
It is selected as 9~11L/h.
The present invention passes through the graphene conductive slurry that above-mentioned steps obtain, and is a kind of highly conductive graphene conductive slurry, this
The performance and structure of the highly conductive graphene is not particularly limited in invention, with highly conductive stone well known to those skilled in the art
The performance and structure of black alkene, those skilled in the art, which carry out preparation according to aforementioned preparation process, can be obtained highly conductive graphite
The performance and structure of graphene in alkene electrocondution slurry, the highly conductive graphene in highly conductive graphene conductive slurry of the present invention
Flaky, thickness, which is preferably less than, is equal to 5nm, is more preferably less than equal to 4nm, is more preferably less than equal to 3nm.This hair
The bright graphene is with a thickness of the random average thickness for choosing 20 lamellas measured by atomic force microscope.
Highly conductive graphene of the present invention, carbon content are measured by elemental analysis, and carbon content is preferably greater than or equal to 99.5%.
Highly conductive graphene of the present invention, conductivity are measured by four probe conduction rate methods of testing, and conductivity is preferably greater than
40000S/m is more preferably higher than equal to 45000S/m, is more preferably higher than equal to 50000S/m, can more reach 70000S/
m。
Above-mentioned steps of the present invention provide a kind of electrocondution slurry containing highly conductive graphene, and the present invention has selected low temperature normal
The liquid phase stripping method of pressure, it is creative using graphite-solvent mixing-ultrasonic disperse-super-high-pressure homogenization method, it is further excellent
Choosing uses small molecule intercalation-high-temperature expansion Graphitic pretreatment mode, by first preparing graphene nanometer sheet, then prepares again steady
Fixed graphene conductive slurry, can in a mild condition quickly, prepare graphene at low cost.And stone prepared by the present invention
Black alkene has complete lamellar structure, is not surface modified, keeps the intrinsic feature of two-dimensional slice.Stone prepared by the present invention
Black alkene electrocondution slurry has the characteristics that high conductivity, high stability, further through to the existing insufficient research of commercial electroconductive agent performance,
Graphene conductive slurry is made using the above method using the conductive characteristic that graphene is excellent, is applied to lithium battery anode material
Material, with high rate performance, the cycle life etc. for significantly improving lithium battery.Electrocondution slurry electric conductivity of the invention is excellent, and dispersion is equal
It is even, stability is good, and simple process, easy to accomplish, be suitble to high-volume system by graphene conductive slurry.
The experimental results showed that highly conductive graphene slurry prepared by the present invention, carbon content is more than or equal to 99.5%, conductivity
Greater than 50000S/m, 70000S/m can be reached, at a high temperature of 60 DEG C, storage 48h or more can be stablized.
In order to further illustrate the present invention, with reference to embodiments to a kind of graphene conductive slurry provided by the invention
Preparation method is described in detail, but it is to be understood that these embodiments are to carry out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, only to further illustrate the features and advantages of the present invention,
Rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Comparative example 1
Raw material are 1000 mesh natural graphites (Qingdao Dong Kai graphite Co., Ltd).By 10g graphite and 50g carbonic acid sodium dihydrogen
Mixing is scattered in 100g water, and mixed liquor mechanical stirring is reacted 20 hours at room temperature, is added the dilution of 400g water, is centrifuged
To intercalated graphite.Intercalated graphite is placed in 1000 DEG C of Muffle furnace, expands 30s.Graphite dispersion after 5g expansion is in 5L N- first
In base pyrrolidones, 800W ultrasound removes 8h, 300rmp ball milling 2h, is centrifuged washing and drying, obtains highly conductive graphene.
The highly conductive graphene of comparative example 1 of the present invention preparation is characterized.
Referring to Fig. 1, Fig. 1 is the atomic force microscopy of the highly conductive graphene of comparative example 1 of the present invention preparation.
It is shown by the atomic force microscopy of Fig. 1, graphene sheet layer has smooth lamellar structure, and planar dimension is in 6 μ
M or so is not surface modified, and keeps the intrinsic feature of two-dimensional slice, thus has preferable electric conductivity.
Thickness sensitivity is carried out to the highly conductive graphene of comparative example 1 of the present invention preparation.
Test method: graphene sample thickness is tested to obtain by PARK NX-10 atomic force microscope.
Referring to fig. 2, the thickness that Fig. 2 is measured for the highly conductive graphene of comparative example 1 of the present invention preparation by atomic force microscope
Spend data and curves.
It can be obtained by the data analysis in Fig. 2, graphene thickness is in 3nm hereinafter, the number of plies is within 10 layers.
Elemental analysis is carried out to the highly conductive graphene of preparation of the embodiment of the present invention.
Test method: the elemental analysis of graphene sample is tested to obtain by ELEMENTAR elemental analyser.
Referring to table 1, table 1 is the Elemental analysis data of the highly conductive graphene of comparative example 1 of the present invention preparation.
Table 1
| Comparative example 1 | |
| C% | 99.414 |
| H% | 0.45 |
| O% | 0.136 |
| N% | 0 |
| S% | 0 |
As shown in Table 1, the carbon content for the highly conductive graphene that prepared by comparative example 1 of the present invention is more than or equal to 99.3%, wherein
The carbon content of highly conductive graphene prepared by comparative example 1 of the present invention has reached 99.414%.
Conductivity is measured using four probe conduction rate methods of testing to the highly conductive graphene of comparative example 1 of the present invention preparation.
Test method: the conductivity of graphene sample is by being pressed into the disk that diameter is 10mm for sample, by Suzhou crystalline substance
Four probe conduction rate tester of lattice is tested to obtain.
The conductivity of highly conductive graphene prepared by comparative example 1 of the present invention has reached 51000S/m.
The stability of the highly conductive graphene of comparative example 1 of the present invention preparation is tested.
Test method: graphene sample is imported in closed transparent sample bottle, is placed in 60 DEG C of baking oven, observes sample
Shelf-stability.
After placing three days, highly conductive graphene layering prepared by comparative example 1 is obvious.
Embodiment 1
8g graphite powder and 1L ethyl alcohol are made into the aqueous solution of 1.5L, its 600r/min mechanical stirring 30min, 1000W is super
Drying is filtered after sound 12h and obtains graphene nanometer sheet, and 3g nanometer sheet, 2g polyvinylpyrrolidone are mixed with 95g ethyl alcohol,
600r/min mechanical stirring 10min, 800W ultrasound 20min, obtains mixed liquor.Again with superhigh-voltage homogenizing machine 1400bar mashing 5
It is secondary, obtain the good graphene conductive slurry of stability.
Referring to Fig. 3, Fig. 3 is the field emission scanning electron microscope photo of highly conductive graphene prepared by the embodiment of the present invention 1.
It is shown by the field emission scanning electron microscope photo of Fig. 3, graphene sheet layer has smooth lamellar structure, and planar dimension exists
It 5 μm or so, is not surface modified, keeps the intrinsic feature of two-dimensional slice, thus there is preferable electric conductivity.
Thickness sensitivity is carried out to highly conductive graphene prepared by the embodiment of the present invention 1.
Test method: graphene sample thickness is tested to obtain by high-resolution-ration transmission electric-lens.
Referring to fig. 4, Fig. 4 is the high-resolution-ration transmission electric-lens photo of highly conductive graphene prepared by the embodiment of the present invention 1.
It can be obtained by the data analysis in Fig. 4, graphene thickness is in 5nm hereinafter, the number of plies is within 20 layers.
Elemental analysis is carried out to the highly conductive graphene of preparation of the embodiment of the present invention.
Test method: the elemental analysis of graphene sample is tested to obtain by ELEMENTAR elemental analyser.
Referring to table 2, table 2 is the Elemental analysis data of highly conductive graphene prepared by the embodiment of the present invention 1.
Table 2
| Embodiment 1 | |
| C% | 99.503 |
| H% | 0.41 |
| O% | 0.087 |
| N% | 0 |
| S% | 0 |
As shown in Table 2, the carbon content for the highly conductive graphene that prepared by the embodiment of the present invention 1 is more than or equal to 99.5%, wherein
The carbon content of highly conductive graphene prepared by the embodiment of the present invention 1 has reached 99.503%.
Conductivity is measured using four probe conduction rate methods of testing to highly conductive graphene prepared by the embodiment of the present invention 1.
Test method: the conductivity of graphene sample is by being pressed into the disk that diameter is 10mm for sample, by Suzhou crystalline substance
Four probe conduction rate tester of lattice is tested to obtain.
The conductivity of highly conductive graphene prepared by the embodiment of the present invention 1 has reached 62500S/m.
The stability of highly conductive graphene prepared by the embodiment of the present invention 1 is tested.
Test method: graphene sample is imported in closed transparent sample bottle, is placed in 60 DEG C of baking oven, observes sample
Shelf-stability.
Highly conductive graphene prepared by the embodiment of the present invention 1 can reach 30 days without obvious layering with this condition.Surely
It is qualitative preferable.
Embodiment 2
15g graphite powder and 1L ethyl alcohol are made into the aqueous solution of 1.5L, its 400r/min mechanical stirring 30min, 2000W is super
Drying is filtered after sound 3h and obtains graphene nanometer sheet, and 7g nanometer sheet, 3g Vingon are mixed with 90g dimethyl acetamide,
700r/min mechanical stirring 20min, 1000W ultrasound 30min, obtains mixed liquor.Again with superhigh-voltage homogenizing machine 800bar mashing 8
It is secondary, obtain the good graphene conductive slurry of stability.
Referring to Fig. 5, Fig. 5 is the field emission scanning electron microscope photo of highly conductive graphene prepared by the embodiment of the present invention 2.
It is shown by the field emission scanning electron microscope photo of Fig. 5, graphene sheet layer has smooth lamellar structure, and planar dimension exists
It 5 μm or so, is not surface modified, keeps the intrinsic feature of two-dimensional slice, thus there is preferable electric conductivity.
Thickness sensitivity is carried out to highly conductive graphene prepared by the embodiment of the present invention 2.
Test method: graphene sample thickness is tested to obtain by high-resolution-ration transmission electric-lens.
Referring to Fig. 6, Fig. 6 is the high-resolution-ration transmission electric-lens photo of highly conductive graphene prepared by the embodiment of the present invention 2.
It can be obtained by the data analysis in Fig. 6, graphene thickness is in 5nm hereinafter, the number of plies is within 20 layers.
Elemental analysis is carried out to the highly conductive graphene of preparation of the embodiment of the present invention.
Test method: the elemental analysis of graphene sample is tested to obtain by ELEMENTAR elemental analyser.
Referring to table 3, table 3 is the Elemental analysis data of highly conductive graphene prepared by the embodiment of the present invention 2.
Table 3
| Embodiment 2 | |
| C% | 99.464 |
| H% | 0.45 |
| O% | 0.086 |
| N% | 0 |
| S% | 0 |
As shown in Table 3, the carbon content for the highly conductive graphene that prepared by the embodiment of the present invention 2 is more than or equal to 99.4%, wherein
The carbon content of highly conductive graphene prepared by the embodiment of the present invention 2 has reached 99.464%.
Conductivity is measured using four probe conduction rate methods of testing to highly conductive graphene prepared by the embodiment of the present invention 2.
Test method: the conductivity of graphene sample is by being pressed into the disk that diameter is 10mm for sample, by Suzhou crystalline substance
Four probe conduction rate tester of lattice is tested to obtain.
The conductivity of highly conductive graphene prepared by the embodiment of the present invention 2 has reached 63100S/m.
The stability of highly conductive graphene prepared by the embodiment of the present invention 2 is tested.
Test method: graphene sample is imported in closed transparent sample bottle, is placed in 60 DEG C of baking oven, observes sample
Shelf-stability.
To highly conductive graphene prepared by the embodiment of the present invention 2, with this condition, 30 days can be reached without obvious layering.
Stability is preferable.
Embodiment 3
20g graphite powder and 1L ethyl alcohol are made into the aqueous solution of 1.5L, its 600r/min mechanical stirring 20min, 3000W is super
Drying is filtered after sound 6h and obtains graphene nanometer sheet, by 4g nanometer sheet, 4g neopelex and 92gN- crassitude
Ketone mixing, 600r/min mechanical stirring 20min, 1000W ultrasound 20min obtain mixed liquor.Superhigh-voltage homogenizing machine 400bar is used again
Mashing 12 times, obtains the good graphene conductive slurry of stability.
Referring to Fig. 7, Fig. 7 is the field emission scanning electron microscope photo of highly conductive graphene prepared by the embodiment of the present invention 3.
It is shown by the field emission scanning electron microscope photo of Fig. 7, graphene sheet layer has smooth lamellar structure, and planar dimension exists
It 5 μm or so, is not surface modified, keeps the intrinsic feature of two-dimensional slice, thus there is preferable electric conductivity.
Thickness sensitivity is carried out to highly conductive graphene prepared by the embodiment of the present invention 3.
Test method: graphene sample thickness is tested to obtain by high-resolution-ration transmission electric-lens.
Referring to Fig. 8, Fig. 8 is the high-resolution-ration transmission electric-lens photo of highly conductive graphene prepared by the embodiment of the present invention 3.
It can be obtained by the data analysis in Fig. 8, graphene thickness is in 3nm hereinafter, the number of plies is within 20 layers.
Elemental analysis is carried out to the highly conductive graphene of preparation of the embodiment of the present invention.
Test method: the elemental analysis of graphene sample is tested to obtain by ELEMENTAR elemental analyser.
Referring to table 4, table 4 is the Elemental analysis data of highly conductive graphene prepared by the embodiment of the present invention 3.
Table 4
| Embodiment 3 | |
| C% | 99.536 |
| H% | 0.39 |
| O% | 0.074 |
| N% | 0 |
| S% | 0 |
As shown in Table 4, the carbon content for the highly conductive graphene that prepared by the embodiment of the present invention 3 is more than or equal to 99.5%, wherein
The carbon content of highly conductive graphene prepared by the embodiment of the present invention 3 has reached 99.536%.
Conductivity is measured using four probe conduction rate methods of testing to highly conductive graphene prepared by the embodiment of the present invention 3.
Test method: the conductivity of graphene sample is by being pressed into the disk that diameter is 10mm for sample, by Suzhou crystalline substance
Four probe conduction rate tester of lattice is tested to obtain.
The conductivity of highly conductive graphene prepared by the embodiment of the present invention 3 has reached 69800S/m.
The stability of highly conductive graphene prepared by the embodiment of the present invention 3 is tested.
Test method: graphene sample is imported in closed transparent sample bottle, is placed in 60 DEG C of baking oven, observes sample
Shelf-stability.
To highly conductive graphene prepared by the embodiment of the present invention 3, with this condition, 30 days can be reached without obvious layering.
Stability is preferable.
Detailed Jie has been carried out to a kind of preparation method of high-stability graphene electrocondution slurry provided by the invention above
It continues, used herein a specific example illustrates the principle and implementation of the invention, and the explanation of above embodiments is only
Be be used to help to understand method and its core concept of the invention, including best mode, and but also this field any skill
Art personnel can practice the present invention, including any device or system of manufacture and use, and implement the method for any combination.It should
It points out, it for those skilled in the art, without departing from the principle of the present invention, can also be to this hair
Bright some improvement and modification can also be carried out, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.The present invention is special
The range of benefit protection is defined by the claims, and may include those skilled in the art it is conceivable that other embodiments.Such as
These other embodiments of fruit have the structural element for being not different from claim character express, or if they include and power
Equivalent structural elements of the character express without essence difference that benefit requires, then these other embodiments should also be included in claim
In the range of.
Claims (10)
1. a kind of preparation method of graphene conductive slurry, which comprises the following steps:
1) it after being removed graphite dispersing solution under conditions of ultrasound, then separates, obtains graphene nanometer sheet；
2) after being mixed graphene nanometer sheet, dispersing agent and solvent that above-mentioned steps obtain, pre- slurry is obtained；
3) after the pre- slurry for obtaining above-mentioned steps carries out homogeneous mashing, graphene conductive slurry is obtained.
2. preparation method according to claim 1, which is characterized in that the graphite in the graphite dispersing solution includes graphite
One of powder, crystalline flake graphite, artificial graphite, expansible graphite and expanded graphite are a variety of；
The mass concentration of graphite is 0.5%~5% in the graphite dispersing solution；
Solvent in the graphite dispersing solution includes water and organic solvent miscible with water.
3. preparation method according to claim 2, which is characterized in that the organic solvent miscible with water include methanol,
Ethyl alcohol, ethylene glycol, glycerol, acetone, tetrahydrofuran, dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone and diformazan
One of base sulfoxide is a variety of；
Mass concentration of the organic solvent miscible with water in the graphite dispersing solution is 30%~70%；
The power of the ultrasound is 600~3000W；The time of the ultrasound is 1~20h；
It further include drying steps after the separation.
4. preparation method according to claim 1, which is characterized in that the mode of the removing includes stirring, shearing, ball milling
Be sanded one of or it is a variety of；
The phosphorus content of the graphene nanometer sheet is more than or equal to 98%；
The graphene nanometer sheet with a thickness of be less than or equal to 5nm；
The piece diameter of the graphene nanometer sheet is 1~20 μm.
5. preparation method according to claim 1, which is characterized in that the dispersing agent includes polyvinylpyrrolidone, gathers
One of vinylidene chloride, polypropylene, cetyl trimethylammonium bromide and neopelex are a variety of；
The solvent includes water, ethyl alcohol, acetone, dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone and dimethyl
One of sulfoxide is a variety of；
In the pre- slurry, the mass concentration of the dispersing agent is 0.2%~10%；
In the pre- slurry, the mass concentration of the graphene nanometer sheet is 1%~10%.
6. preparation method according to claim 1, which is characterized in that the homogeneous is super-high-pressure homogenization；
The number of the homogeneous is 1~20 time；
The conductivity of the graphene conductive slurry is more than or equal to 40000S/m.
7. preparation method according to claim 6, which is characterized in that the pressure of the super-high-pressure homogenization be 400~
1500bar；
The processing speed of the super-high-pressure homogenization is 5~15L/h.
8. preparation method according to claim 1, which is characterized in that the graphite is to pass through pretreated graphite；
The pretreated step are as follows:
A after) being reacted graphite and small molecule intercalator, intercalated graphite is obtained；
B) intercalated graphite for obtaining above-mentioned steps is after high-temperature expansion, the graphite that obtains that treated.
9. preparation method according to claim 8, which is characterized in that the granularity of the graphite is 50~10000 mesh；
The carbon content of the graphite is more than or equal to 70%；
The small molecule intercalator includes small molecule high temperature decomposable compound；
The time of the reaction is 10~30 hours；The temperature of the reaction is 0~40 DEG C.
10. preparation method according to claim 9, which is characterized in that the small molecule intercalator include sulfuric acid, nitric acid,
One in urea, sodium bicarbonate, carbonic acid sodium dihydrogen, disodium bicarbonate, oxalic acid, phosphoric acid, perchloric acid, periodic acid and trifluoromethanesulfonic acid
Kind is a variety of；
The mass ratio of the graphite and small molecule intercalator is 1:(1~5)；
The temperature of the high-temperature expansion is 500~1200 DEG C；
The time of the high-temperature expansion is 5~60 seconds.
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