CN110330012A - The preparation method of high concentration graphene aqueous liquid dispersion and self-dispersing graphene powder - Google Patents

The preparation method of high concentration graphene aqueous liquid dispersion and self-dispersing graphene powder Download PDF

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CN110330012A
CN110330012A CN201910671352.2A CN201910671352A CN110330012A CN 110330012 A CN110330012 A CN 110330012A CN 201910671352 A CN201910671352 A CN 201910671352A CN 110330012 A CN110330012 A CN 110330012A
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graphene
graphite
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dispersing
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周建
丁古巧
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Shanghai Ewang Material Technology Co Ltd
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • C01B32/19Preparation by exfoliation
    • CCHEMISTRY; METALLURGY
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/194After-treatment
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
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    • C01B2204/28Solid content in solvents

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Abstract

The present invention relates to the preparation methods of a kind of high concentration graphene aqueous liquid dispersion and self-dispersing graphene powder.The preparation method of the graphene aqueous liquid dispersion includes: the aqueous solution of (1) configuration dispersing agent and inorganic salts, lamellar graphite is added in the aqueous solution, lamellar graphite suspension is made, carry out shearing dispersion to the suspension;(2) high concentration graphene aqueous liquid dispersion is obtained using the lamellar graphite suspension after one of milling treatment of colloid, high-pressure homogeneous processing, ultrasonic treatment, the shock of high pressure microjet, milled processed or the processing shearing dispersion of a variety of mechanical systems.High concentration graphene aqueous liquid dispersion is spray-dried or is freeze-dried up to self-dispersing graphene powder.Graphene aqueous liquid dispersion concentration produced by the present invention is high, and for the self-dispersing graphene powder number of plies less than 10 layers, degree of oxidation is low, and favorable dispersibility when being dispersed in water again.

Description

The preparation method of high concentration graphene aqueous liquid dispersion and self-dispersing graphene powder
Technical field
The invention belongs to grapheme material fields, more specifically to high concentration graphene aqueous liquid dispersion and self-dispersing The composition of the preparation method and dispersing agent of graphene powder and inorganic salts prepare high concentration graphene aqueous liquid dispersion and Purposes in self-dispersing graphene powder.
Background technique
Graphene is a kind of tightly packed carbonaceous material at monatomic bi-dimensional cellular shape lattice structure of carbon atom, due to it The property and its unprecedented performance of ultra-thin, two-dimentional (2D), graphene, which has become, studies most hot nano material.Its superelevation (single-layer graphene specific surface area theoretical calculation is 2620m to specific surface area2/ g), excellent electron mobility (200000cm2/(V· S)), high thermal conductivity (thermal coefficient is up to 5300W/mk), superpower mechanical property and good biocompatibility, make it It can be applied to the materials such as conductive, thermally conductive, antibacterial.
Graphene is in practical applications, if it is desired to play its excellent performance, it is necessary to is dispersed into monolithic or primary grain Sub- state.However, it is desirable to realize that the high dispersive of graphene is extremely difficult, since graphene itself has neither hydrophilic and not oleophylic Structure feature, and the π-π structure of graphene and strong Van der Waals force make graphene easily reunite, and aggregate is difficult to It separates again.General dispersant molecule is again more difficult to form stronger physisorption with graphene, so using surface-active The physical means of dispersed graphite alkene will be also limited;Graphene oxide is realized by chemical modification to be dispersed, and place is then restored again Reason, but chemical modification, certainly will interfere or destroy to a certain extent the integrality of π-π, to reduce or lose eigenstate graphite The excellent properties of alkene.
Currently, the concentration of graphene dispersion system is relatively low, it can accomplish that concentration is in aqueous dispersion system highest 0.9mg/mL, organic solvent system can accomplish that concentration is 1.2mg/mL.Moreover, even if in aqueous or organic solvent body Can be well dispersed in system, but after drying becomes powder, major part is all difficult to well dispersed again.And organic solvent is unfavorable It is at high cost in environmental protection.Therefore exploitation graphene dispersion system has extraordinary prospect.Chinese patent CN 109553095 A [yellow treasured select etc., a kind of denomination of invention: preparation method of high concentration high concentration graphene aqueous solution: publication date April 2 in 2019 Day] disclose it is a kind of using the dispersing agents dispersion grinding graphene such as sodium carboxymethylcellulose, it is 30~50mg/ml that concentration, which is made, The dispersion system that solid content is 4~5%.But it uses graphene directly to be dispersed, cost is in contrast higher, together When its drying after redisperse effect do not refer to.
106395806 A of Chinese patent CN [Li Yongfeng etc., denomination of invention: a kind of hydrophilic graphene and its preparation side Method: publication date on 2 15th, 2017] disclose it is a kind of using the surfactant-disperseds stone such as neopelex (SDBS) Ink is passed through gaseous state intercalation medium in ball grinder, and the air inflow by adjusting gaseous state intercalation medium controls pressure in 2- System temperature is risen to 35-150 DEG C of progress ball milling original position accessory molecule intercalation, reaction terminates at this pressure by 12MPa After obtain hydrophilic graphene.The method uses high-temperature and high-pressure conditions, and manufacturing condition is harsh, and the graphene prepared point Scattered concentration only has 1mg/ml.
Therefore it provides a kind of high concentration graphene aqueous liquid dispersion liquid and can be in water with good self-dispersing Graphene powder has become the technical issues of graphene application field urgent need to resolve.
Summary of the invention
It is relatively low for the concentration of existing graphene dispersion system, especially the concentration of watersoluble plumbago alkene dispersing agent body compared with It is low, and dispersibility poor disadvantage when the graphene powder as made from graphene dispersion system is dispersed again in solvent, this The purpose of invention one side is to provide a kind of preparation method of high concentration graphene aqueous liquid dispersion.
The preparation method of high concentration graphene aqueous liquid dispersion of the invention the following steps are included:
(1) in the aqueous solution for configuring dispersing agent and inorganic salts, lamellar graphite is added in the aqueous solution, stratiform stone is made The suspension of ink, carries out shearing dispersion to the suspension;
(2) using one in milling treatment of colloid, high-pressure homogeneous processing, ultrasonic treatment, the shock of high pressure microjet, milled processed The suspension of lamellar graphite after kind or the processing shearing dispersion of a variety of mechanical systems obtains highly concentrated stone with mechanical stripping lamellar graphite Black alkene aqueous liquid dispersion.
In a specific embodiment, in step (1), the lamellar graphite be selected from natural flake graphite, synthetic graphite, can Expanded graphite, expanded graphite, intercalated graphite, graphite nano plate, electrochemical pre-treatment graphite, aquadag, highly oriented thermal cracking One of graphite composite powder is a variety of;Preferably, which is expanded graphite and/or electrochemical treatments graphite.
In a specific embodiment, in step (1), which is selected from neopelex, dodecyl Sodium sulphate, alkyl glycosides, sodium taurocholate, lignosulfonates, sapn, cellulose, styrene sulfonate, polyvinylpyrrolidone etc. One of or it is a variety of;Preferably, which is sodium lignin sulfonate.
In a specific embodiment, in step (1), which is selected from sulfate, chloride, nitrate, sulfonic acid One of salt, carbonate, phosphate are a variety of;Preferably, which is sodium sulphate, potassium carbonate and/or sodium chloride;It is more excellent Selection of land, the inorganic salts are sodium sulphate.
In a specific embodiment, dispersing agent is selected from potassium carboxymethylcellulose, and inorganic salts are selected from potash water Solution.In another embodiment of the invention, and dispersing agent is selected from lignocellulose ammonium, inorganic salts sodium sulphate Water.In another embodiment of the invention, dispersing agent is selected from polyvinylpyrrolidone and inorganic salts are selected from chlorination Sodium and water.
In a specific embodiment, in step (1), the weight ratio of the dispersing agent and the inorganic salts is 1:1-100:1; Preferably, the weight ratio of dispersing agent and inorganic salts is 1:1-10:1.
In a specific embodiment, in step (1), the weight ratio of the lamellar graphite and the dispersing agent is 1:0.01- 1:10;Preferably, the lamellar graphite and the weight ratio of the dispersing agent are 5:1-10:1.
In a specific embodiment, in step (1), the weight ratio of the lamellar graphite and the inorganic salts is 1:0.01- 1:0.1;Preferably, the lamellar graphite and the weight ratio of the inorganic salts are 60:1-10:1.
In a specific embodiment, in step (1), the weight ratio of the lamellar graphite and water is 1:8-1:100;It is preferred that The weight ratio of ground, the lamellar graphite and water is 1:10-1:50.
In a specific embodiment, the lamellar graphite suspension in step (2) after mechanical system processing shearing dispersion Temperature be 10-80 DEG C;It is highly preferred that the temperature is 20-50 DEG C.
In a specific embodiment, the lamellar graphite suspension in step (2) after mechanical system processing shearing dispersion Time be 1-24h;Preferably, which is 2-10h.
Graphite in the graphene aqueous liquid dispersion of the preparation method preparation of high concentration graphene aqueous liquid dispersion of the invention Alkene concentration is not less than 50mg/ml.
In a specific embodiment, graphene in the high concentration graphene aqueous liquid dispersion of method of the invention preparation Concentration is 80mg/ml.In another embodiment, the high concentration graphene aqueous liquid dispersion of method of the invention preparation Middle graphene concentration is 50mg/ml.
Another aspect of the present invention provides a kind of preparation method of self-dispersing graphene powder, and this method includes by above-mentioned height The graphene aqueous liquid dispersion of the preparation method preparation of concentration graphene aqueous liquid dispersion is spray-dried or is freeze-dried i.e. Available from dispersed graphite alkene powder.
The layer of graphene in the self-dispersing graphene powder of the preparation method preparation of self-dispersing graphene powder of the invention Number is 1-10 layers.
Further aspect of the present invention provides dispersing agent and the composition of inorganic salts is preparing high concentration graphene aqueous dispersion Purposes in liquid and self-dispersing graphene powder, in the composition, the weight ratio of dispersing agent and inorganic salts is 1:1-100:1.
In a specific embodiment, which is selected from neopelex, lauryl sodium sulfate, alkyl One of glucosides, sodium taurocholate, lignosulfonates, sapn, cellulose, styrene sulfonate, polyvinylpyrrolidone etc. or It is a variety of;
In a specific embodiment, the inorganic salts be selected from sulfate, chloride, nitrate, sulfonate, carbonate, One of phosphate, hydroxide are a variety of;Preferably, which is sodium sulphate, potassium carbonate and/or sodium chloride;It is more excellent Selection of land, the inorganic salts are sodium sulphate.
In a specific embodiment, dispersing agent is selected from potassium carboxymethylcellulose, and inorganic salts are selected from potash water Solution.In another embodiment of the invention, dispersing agent is selected from lignocellulose ammonium, and inorganic salts sodium sulphate Water.In another embodiment of the invention, dispersing agent is selected from polyvinylpyrrolidone and inorganic salts are selected from chlorination Sodium water.
In a preferred embodiment, in the composition, the mass ratio of dispersing agent and inorganic salts is 1:1-10:1.
The present invention prepare resulting self-dispersing graphene powder can be applied to Material reinforcement, conduction, thermally conductive, anti-corrosion, resist it is quiet Electricity, far infrared, biologic medical etc..
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of graphene prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of graphene prepared by the embodiment of the present invention 2.
Fig. 3 is the scanning electron microscope (SEM) photograph of graphene prepared by the embodiment of the present invention 3.
Fig. 4 is the transmission electron microscope picture of graphene prepared by the embodiment of the present invention 3.
Fig. 5 is the scanning electron microscope (SEM) photograph of graphene prepared by the embodiment of the present invention 4.
Fig. 6 is aqueous liquid dispersion photo figure of the product of embodiment 1 according to the weight ratio of graphene and water for 5:95 configuration.
Specific embodiment
Relatively low for the concentration of graphene dispersion system in the prior art, especially watersoluble plumbago alkene disperses The concentration of agent body is lower, and dispersibility is poor when the graphene powder as made from graphene dispersing solution is dispersed again in solvent The shortcomings that, lamellar graphite is added in the aqueous solution containing dispersing agent and inorganic salts by the present inventor by in-depth study, into Row dispersion (for example, shearing) then carries out high-pressure homogeneous, ultrasonic, sand milling or high pressure microjet mode to suspension laminate Graphite is hit, removes to obtain highly concentrated nano-graphene aqueous liquid dispersion, which is spray-dried It obtains or is freeze-dried up to the good graphene powder of self-dispersing.Method of the invention makees solvent with water, be it is environmental-friendly, Substantially non-environmental-pollution.And the concentration of graphene is high in the graphene aqueous liquid dispersion prepared, and good dispersion, the number of plies is few, Defect is few, and a small amount of dispersing agent and inorganic salts reduce waste water brought by washing without separation in graphene aqueous liquid dispersion, The present invention is completed on the basis of this completes the present invention on this basis.
In the preparation method of graphene aqueous liquid dispersion of the invention certain density point first can be dispersed by lamellar graphite In the aqueous solution of powder and inorganic salts, sheared using shearing equipment so that lamellar graphite is dispersed more evenly.Of the invention In one specific embodiment, the time by shearing dispersion lamellar graphite is 10-40 minutes, and temperature is 10-80 DEG C, more preferably 20-40℃。
In the preparation method of graphene aqueous liquid dispersion of the invention, the stratiform after shearing dispersion is handled using mechanical system During the suspension of graphite is with mechanical stripping lamellar graphite, the combination of one or more mechanical system processing can be used.Example Such as, in the specific embodiment of the present invention, mechanical stripping lamellar graphite alkene is to hang the lamellar graphite after shearing dispersion The advanced horizontal high voltage homogenization of supernatant liquid, is then sanded with sand mill.In another embodiment of the invention, machine Tool stripped laminar graphene is that the lamellar graphite suspension after shearing dispersion is first sanded with sand mill, then micro- with high pressure Jet homogenizer is hit.In another embodiment of the invention, mechanical stripping lamellar graphite alkene is that will shear Lamellar graphite suspension after dispersion is first ultrasonically treated, then is ground with sand mill, and high pressure homogenizer is then used Homogenization is carried out, is finally hit with high pressure Microfluidizer.In another embodiment of the invention, machine Tool stripped laminar graphene be will shearing dispersion after lamellar graphite suspension be lamellar graphite suspension is first used sand mill into Row grinding, is then hit with high pressure Microfluidizer.
In the specific embodiment of the present invention, the lamellar graphite temperature after mechanical system processing shearing dispersion is 10-80 DEG C, more preferable 20-40 DEG C.In the specific embodiment of the present invention, high pressure homogenizer carry out homogenization when Between be 1-3h, preferably 2h, pressure 100-200MPa, preferably 150MPa.In the specific embodiment of the present invention, sand is used The time that grinding machine carries out sanded treatment is 3-5h, preferably 4h, revolving speed 1500-3000r/min, preferably 2000r/min.In this hair It is 0.5-2h with the time that high pressure homogenizer carries out homogenization in a bright specific embodiment, preferably 1h, pressure is 150-300MPa, preferably 200-250MPa.In the specific embodiment of the present invention, it is ultrasonically treated with Ultrasound Instrument Ultrasonic power is 15-25KW, preferably 20KW, and being ultrasonically treated is 3-5h, preferably 4h.
Lamellar graphite of the invention can be selected from natural flake graphite, synthetic graphite, expansible graphite, expanded graphite, intercalation Graphite, electrochemical treatments graphite, graphite nano plate, aquadag, highly oriented thermal cracking graphite composite powder it is one or more, it is more excellent Choosing is expanded graphite, electrochemical treatments graphite etc..
Electrochemical treatments graphite of the invention the preparation method comprises the following steps: using crystalline flake graphite material as the material of anode, oxalic acid Mixed solution with hydrogen peroxide carries out cell reaction realization and shells to the electrochemistry of anode, centrifugal drying obtains graphite as electrolyte Alkene presoma (referring to, 107235487 A of Chinese patent CN, patent of invention title: the preparation method of graphene, fourth is ancient skilful etc., Publication date: on October 10th, 2017).
In the present invention, high concentration refers to that concentration of the graphene in its aqueous liquid dispersion should not be below 50mg/ml.
In the present invention, high-pressure homogeneous processing can be realized by high pressure homogenizer, and milled processed can pass through ball mill, sand mill It realizes, ultrasonic treatment can be realized by Ultrasound Instrument.
In the present invention, " inorganic salts " are relatively good inorganic salts of dissolubility in cold water at normal temperature, for example, in solubility Greater than 10g/L, preferably greater than 100g/L, more preferable 1000g/L.
In the present invention, " dispersing agent " is environmentally friendly, easily decomposition, and to operator's nonhazardous.
Inorganic salts of the invention with dispersing agent for compounding in aqueous solution.Dispersing agent of the invention is a kind of enough resistance to inorganic The surfactant of salt when concentration is low in aqueous solution, exists with molecular state, when concentration is met or exceeded to a certain degree When, surfactant molecule can be associated with micella, at this point, many physical properties such as surface tension of solution, molar conductance, infiltration There is turning point in the variation tendencies such as pressure.When, there are when inorganic salts, inorganic salts can Surfactant point in surfactant solution Son is associated with micella and has an impact.Counter ion in inorganic salts can neutralize the hydrophilic elementary charge of surfactant moieties, reduce mutually electricity The thickness of micella diffusion electric double layer is reduced in position, so that micella be made to be easier to be formed, CMC reduces (surfactant shape in aqueous solution Minimum concentration at surfactant needed for micella is known as critical micelle concentration, is indicated with CMC) [Zhao Guoxi surfactant object The Beijing Physicochemical [M]: BJ University Press, 1984].Therefore a certain amount of inorganic salts are added in the solution, it is living using surface Electrostatic interaction and Van der Waals force between property agent and inorganic salts, can reduce the additive amount of surfactant, while inorganic salts can With intercalated graphite, in this way, the removing of lamellar graphite is easier by the synergistic effect of surfactant and inorganic salts, most end form At high concentration graphene aqueous solution.
In the present invention, " a variety of " or " several " refer to two or more.
In the present invention, " high concentration " refers to that the concentration of graphene in graphene dispersing solution should not be below 50mg/ml.
Method of the invention has the advantages that
1. method of the invention is compounded using surfactant and dispersing agent, using surfactant and inorganic salts it Between electrostatic interaction and Van der Waals force reduce the additive amount of surfactant, while inorganic salts can be with intercalated graphite, with machinery Physical method carries out mechanical stripping to Multi-layer graphite, and peeling effect is good;
2. the concentration of graphene aqueous liquid dispersion prepared by method of the invention reaches as high as 80mg/ml, in this high concentration Under, slurry still keeps good fluidity;The present invention prepares the number of plies of the graphene of resulting self-dispersing Graphene powder less than 10 Layer, degree of oxidation is low, and is scattered in favorable dispersibility when in solvent (for example, water) again.
3. method simple production process of the invention, production cost is low, being capable of the highly concentrated water-soluble graphene of mass production. Graphene obtained is easy to separate and purify, or even is directly spray-dried, be can be obtained without separation in certain application fields Graphene powder with good dispersion.
Present invention will be further explained below with reference to specific examples, it should be understood that following instance is merely provided for of the invention Best practices mode is described in further detail, the range that should not be construed as limiting the invention.In the following example not The experimental method for indicating actual conditions, usually according to conventional practices and condition, or according to the normal condition proposed by manufacturer. Unless otherwise stated, otherwise percentage and number are calculated by weight.Instrument used in electron microscope analysis is scanned in the following example Device is: producer: TESCAN CHINA, model: RISE Microscope), instrument used in transmission electron microscope analysis is: (FET- Tencnai G2F20S-7WIN)
Embodiment 1
The preparation of 1.1 high concentration graphene aqueous liquid dispersions:
Using crystalline flake graphite powder (Qingdao day Sheng Da graphite Co., Ltd, model: 300 mesh) as removing raw material, first Certain density potassium carboxymethylcellulose, wet chemical are configured, then crystalline flake graphite powder is added in the aqueous solution, Middle crystalline flake graphite powder, potassium carboxymethylcellulose, potassium carbonate, water weight ratio be 8:0.8:0.8:90.4, by mixed liquor into Row shearing dispersion 15 minutes, crystalline flake graphite dispersion liquid is obtained, homogenization 2h is then carried out using high pressure homogenizer, pressure is Then 150MPa, the thin layer graphite piece tentatively removed are sent to sand mill and continue through sand milling and removed, when sand milling Between be 4h, sand mill revolving speed be 2000r/min, obtain the graphene aqueous liquid dispersion of 80mg/ml.
The preparation of 1.2 self-dispersing graphenes:
By the dry separation of watersoluble plumbago alkene dispersion liquid Direct spraying made from 1.1, obtain graphene powder less than 10 layers, Average piece diameter is 800nm.Electron microscope analysis is scanned to the graphene and obtains image as shown in Figure 1.
Embodiment 2
The preparation of 1.1 high concentration graphene aqueous liquid dispersions:
Using electrochemical treatments graphite composite powder (referring to 107235487 A of Chinese patent CN, patent of invention title: graphene Preparation method, fourth is ancient skilful etc., publication date: prepared by content documented by October 10th, 2017) as removing raw material, Certain density lignocellulose ammonium, aqueous sodium persulfate solution are configured first, and then electrochemical treatments graphite composite powder is added should In aqueous solution, wherein electrochemical treatments graphite composite powder, lignocellulose ammonium, sodium sulphate, water weight ratio be 6:1.2: Mixed liquor is carried out shearing dispersion 15 minutes, electrochemical treatments graphite composite powder dispersion liquid is obtained, then using sand milling by 0.1:92.7 Machine carries out processing 4h, then the thin layer graphite piece tentatively removed is sent to Microfluidizer and carries out shock processing, The matter time is 1h, and the pressure of Microfluidizer is 200MPa, obtains the graphene aqueous liquid dispersion of 50mg/ml.
The preparation of 1.2 self-dispersing graphenes:
By the dry separation of graphene aqueous liquid dispersion Direct spraying made from 1.1, obtain graphene powder less than 10 layers, Average piece diameter is 500nm.Electron microscope analysis is scanned to the graphene and obtains image as shown in Figure 2.
Embodiment 3
The preparation of 1.1 high concentration graphene aqueous liquid dispersions:
(1) first using expanded graphite powder (Qingdao day Sheng Da graphite Co., Ltd, model: 80 mesh) as removing raw material Certain density polyvinylpyrrolidone, sodium-chloride water solution are first configured, then expanded graphite powder is added in the aqueous solution, Wherein expanded graphite powder, polyvinylpyrrolidone, sodium chloride, water weight ratio be 5:0.75:0.2:94.05, will mix Liquid carries out shearing dispersion 15 minutes, obtains expanded graphite dispersion liquid, is then ultrasonically treated using ultrasound, and ultrasonic power is arranged For 20KW, when being ultrasonically treated small 4, then the graphite flake dispersion liquid tentatively removed is sent to sand mill and continues through sand Mill is removed, and the sands milling time is 2h, and sand mill is reported as 2000r/min, be then sent to high pressure Microfluidizer into Row is hit, and time 1h, pressure 280MPa obtain the graphene dispersing solution of 50mg/ml.
The preparation of 1.2 self-dispersing graphenes:
By the dry separation of watersoluble plumbago alkene dispersion liquid Direct spraying made from 1.1, obtain graphene powder less than 10 layers, Average piece diameter is 500nm.Electron microscope analysis is scanned to the graphene and obtains image as shown in Figure 3, which is carried out Transmission electron microscope analysis obtains image as shown in Figure 4.
Embodiment 4
The preparation of 1.1 high concentration graphene aqueous liquid dispersions:
(1) first using nano graphite flakes (Qingdao day Sheng Da graphite Co., Ltd, model: 10000 mesh) as removing raw material Certain density sodium taurocholate, sodium hydrate aqueous solution are first configured, then nano graphite flakes are added in the aqueous solution, wherein nanometer Graphite flake, sodium taurocholate, sodium hydroxide, water weight ratio be 5:0.5:0.1:94.4, by mixed liquor carry out shearing dispersion 15 points Clock obtains nano graphite flakes dispersion liquid, then carries out decentralized processing using colloid mill, revolving speed 10000r/min, decentralized processing is small by 4 When, then the graphite flake dispersion liquid tentatively removed is sent to sand mill and continues through sand milling and removed, the time is sanded For 4h, sand mill is reported as 2500r/min, obtains the graphene dispersing solution of 50mg/ml.
The preparation of 1.2 self-dispersing graphenes:
By the dry separation of watersoluble plumbago alkene dispersion liquid Direct spraying made from 1.1, obtain graphene powder less than 10 layers, Average piece diameter is 600nm.Electron microscope analysis is scanned to the graphene and obtains image as shown in Figure 5.
Embodiment 5
Can be 1:99,3 according to the weight ratio of graphene (as prepared by the embodiment of the present invention 1) and water in closed container: 97,5:95 and 8:92 prepares four graphene dispersing solutions, respectively divides self-dispersing graphene prepared by above-described embodiment 1-3 again It dissipates in water, it is after mixing evenly, closed at room temperature to place 3 months, it is separately recorded in the 0th day, 20 days, 30 days, 45 days, 60 It, the precipitation status of the aqueous liquid dispersions of these graphenes observed of same time of 75 days and 90 days.As a result, it has been found that configuration After solution one day, container bottom has a small amount of undissolved ingredient, i.e., a small amount of precipitating, but passage these graphenes at any time Aqueous liquid dispersion there is no variation, and a small amount of precipitating of container bottom does not increase substantially.
Fig. 6 is dispersion liquid of the product of embodiment 1 according to the weight ratio of graphene and water for 5:95 configuration.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document It is incorporated as with reference to such.Furthermore another to understand, after reading the above teachings of the present invention, those skilled in the art can To make kind of change to the present invention or modify, such equivalent forms equally fall within model defined by the application the appended claims It encloses.

Claims (12)

1. a kind of preparation method of high concentration graphene aqueous liquid dispersion, which is characterized in that method includes the following steps:
(1) lamellar graphite is added in the aqueous solution and lamellar graphite suspension is made by the aqueous solution for configuring dispersing agent and inorganic salts Liquid carries out shearing dispersion to the suspension;
(2) using one of high-pressure homogeneous processing, ultrasonic treatment, the shock of high pressure microjet, milled processed or a variety of machinery sides Lamellar graphite suspension after formula processing shearing dispersion is with mechanical stripping lamellar graphite to obtain aqueous point of high concentration graphene Dispersion liquid.
2. preparation method according to claim 1, which is characterized in that layered graphite is selected from natural flake graphite, closes It is taken at graphite, expansible graphite, expanded graphite, intercalated graphite, graphite nano plate, electrochemical pre-treatment graphite, aquadag, height To one of thermal cracking graphite composite powder or a variety of.
3. preparation method according to claim 1, which is characterized in that the dispersing agent is selected from, lauryl sodium sulfate, alkane One of base glucosides, sodium taurocholate, lignosulfonates, sapn, cellulose, styrene sulfonate, polyvinylpyrrolidone etc. Or it is a variety of.
4. preparation method according to claim 1, which is characterized in that the inorganic salts are selected from sulfate, chloride, nitric acid One of salt, sulfonate, carbonate, phosphate, hydroxide are a variety of.
5. preparation method according to claim 1, which is characterized in that the weight ratio of the dispersing agent and the inorganic salts is 1:1-100:1。
6. preparation method according to claim 1-5, which is characterized in that mechanical system processing is cut in step (2) The temperature of lamellar graphite suspension after cutting is scattered is 10-80 DEG C.
7. preparation method according to claim 1-5, which is characterized in that the high concentration stone of preparation method preparation The concentration of graphene is not less than 50mg/ml in black alkene aqueous liquid dispersion.
8. a kind of preparation method of self-dispersing graphene powder, which is characterized in that by preparation described in any one of claims 1-6 The graphene aqueous liquid dispersion of method preparation is spray-dried or is freeze-dried i.e. available from dispersed graphite alkene powder.
9. preparation method according to claim 8, which is characterized in that the self-dispersing graphene powder of preparation method preparation The number of plies of middle graphene is 1-10 layers.
10. the composition of dispersing agent and inorganic salts is in preparing high concentration graphene dispersion aqueous and self-dispersing graphene powder Purposes, the weight ratio of dispersing agent and inorganic salts is 1:1-100:1 in the composition.
11. purposes according to claim 10, which is characterized in that the dispersing agent is selected from neopelex, ten Sodium dialkyl sulfate, alkyl glycosides, sodium taurocholate, lignosulfonates, sapn, cellulose, styrene sulfonate, polyvinyl pyrrole One of alkanone etc. is a variety of.
12. purposes according to claim 10, which is characterized in that the inorganic salts are selected from sulfate, chloride, nitric acid One of salt, sulfonate, carbonate, phosphate are a variety of.
CN201910671352.2A 2019-07-24 2019-07-24 The preparation method of high concentration graphene aqueous liquid dispersion and self-dispersing graphene powder Pending CN110330012A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
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CN111285361A (en) * 2020-04-14 2020-06-16 中北大学 High-efficiency liquid-phase mechanical preparation method of low-defect and high-dispersion graphene
CN111591982A (en) * 2020-05-25 2020-08-28 杭州烯创科技有限公司 Physical preparation method of graphene by using crystalline flake graphite as raw material
CN112143072A (en) * 2020-09-02 2020-12-29 新奥(内蒙古)石墨烯材料有限公司 Graphene/polyethylene heat conduction material, preparation method thereof, pipe using heat conduction material and ground source heat pump
CN114014308A (en) * 2021-12-13 2022-02-08 中科悦达(上海)材料科技有限公司 Preparation method of graphene composite material and graphene composite material
CN116375009A (en) * 2022-12-26 2023-07-04 中国科学院福建物质结构研究所 Preparation method of modified graphene

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN110655071A (en) * 2019-10-29 2020-01-07 昂星新型碳材料常州有限公司 Sulfonic group modified graphene, preparation method thereof and application of sulfonic group modified graphene in water-based epoxy coating
CN111285361A (en) * 2020-04-14 2020-06-16 中北大学 High-efficiency liquid-phase mechanical preparation method of low-defect and high-dispersion graphene
CN111591982A (en) * 2020-05-25 2020-08-28 杭州烯创科技有限公司 Physical preparation method of graphene by using crystalline flake graphite as raw material
CN112143072A (en) * 2020-09-02 2020-12-29 新奥(内蒙古)石墨烯材料有限公司 Graphene/polyethylene heat conduction material, preparation method thereof, pipe using heat conduction material and ground source heat pump
CN114014308A (en) * 2021-12-13 2022-02-08 中科悦达(上海)材料科技有限公司 Preparation method of graphene composite material and graphene composite material
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