CN109265712A - The preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated - Google Patents

The preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated Download PDF

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CN109265712A
CN109265712A CN201811038243.9A CN201811038243A CN109265712A CN 109265712 A CN109265712 A CN 109265712A CN 201811038243 A CN201811038243 A CN 201811038243A CN 109265712 A CN109265712 A CN 109265712A
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graphene
polyacrylic acid
conducting particles
composite conducting
particle
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CN109265712B (en
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曾尤
郝亚斌
张藤心
方明赫
英哲
王函
成会明
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Institute of Metal Research of CAS
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The present invention relates to composite conducting technical field, in particular to a kind of preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated.The graphene powder for expanding graft process preparation is distributed in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, oil bath reacts to obtain the graphene of carboxylated；By the carboxylated graphene dispersion into n,N dimethylformamide, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride is added, after ultrasonic disperse, ethylenediamine is added into dispersion liquid, oil bath reacts to obtain amidized graphene.Dry polyacrylic acid particle is placed in the aqueous dispersions of amination graphene, under the action of osmotic pressure and electrostatic attraction, graphene coated is diffused into particle core in the surface of polyacrylic acid particle, and along the gap between strand.The pH value of polyacrylic acid particle and the aqueous dispersions of graphene is adjusted to 1~2, after vacuum drying later, obtains the polyacrylic acid composite conducting particles of graphene Gradient Coated.

Description

The preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated
Technical field
The present invention relates to composite conducting technical field, in particular to a kind of polyacrylic acid composite guide of graphene Gradient Coated The preparation method of charged particle.
Background technique
Conductive filler mainly has metal packing, carbon filler, metal oxide system filler, compounded mix etc., composite conducting Filler then includes powder and fiber of plating metal etc..
Common metallic conductive fillers have silver, copper, nickel, iron etc., in which: silver has both good conductivity and oxidation resistance by force Advantage, but it is expensive, and it is easy to happen ELECTROMIGRATION PHENOMENON under hygrothermal environment, cause silver conductive adhesive resistance unstable；Copper, The inoxidizability such as nickel, iron, corrosion resistance are poor, influence its long-time service.The poorly conductive of metal oxide system filler and anticorrosive Property it is poor, be not suitable for large-scale use.Charcoal system conductive filler, there are commonly carbon black, graphite, carbon fibers etc..These conductive fillers exist There is the defects of low such as conductivity and difficulties in dispersion in practical application, seriously restricts it in the application in electron and electrician field.Cause This, the preparation of high conductivity and cost effective conductive filler increasingly becomes the emphasis of people's research.
Graphene is single layer of carbon atom with sp2The two-dimensional arrangements structure of hydridization connection composition, wherein carbon atom is closely arranged It is listed on honeycomb dot matrix, there is honeycomb or regular hexagon structure.Perfect graphene is ideal two dimensional crystal material, Thickness is only 0.34nm, and graphene prepared by success has ideal structural strength and good electric conductivity, for material Material science, electrical field are significant.There is following benefit as conductive filler using graphene: (1) graphene and common gold The systems such as category, carbon nanotube, conductive black are compared, and have bigger specific surface area, under conditions of obtaining identical electric conductivity, The dosage of conductive filler can be saved；(2) graphene has good ductility, can fabricate according to arbitrary shape；(3) Graphene has good chemical stability.
Other than changing the type of conductive filler, the structure for changing conductive filler is also a heat in conductive filler field Point research direction.There are compound particle, the compound particle of Carbon Materials cladding etc. of plating metal at present, in which: the composite guide of plating metal Charged particle (such as: silver-coated copper powder), surface coating rate is uncertain, and electric conductivity and inoxidizability are also poor；Meanwhile conductive filler exists Oxidation can be freeed during storage, can form layer of oxide layer on conductive filler surface, this also increases when electric current passes through Resistance.The application of these problems limitation me tallic conductive filler.Use novel charcoal material graphene as clad, coats matrix Particle constitutes composite conducting particles, can make full use of the high conductivity and chemical stability of graphene, while effectively solving charcoal The dispersion of material in the base forms conductive path using lesser graphene additive amount, obtains high conductivity.But Simple cladding process, will cause graphene coated rate and does not know, cladding binding force is poor；Meanwhile graphene excess modification, surface Functional group is excessive, seriously affects its electric conductivity；The size control of conductive composite particle is poor.These problems limit graphene coated The use of conductive filler.
For example, Chinese invention patent application (patent publication No. CN107793679A, applying date 2017.11.30) uses It is the core of three-layer nuclear shell nanoparticle for silica, silane coupling agent is grafted to nanoparticle surface, then by graphite oxide Alkene cladding gets on, and the oxygen groups that coupling agent grafting connects graphene with covalent modification are sacrificed the lamella integrality of graphene and led Electrically.Chinese invention patent application (patent publication No. CN106532074A, applying date 2016.11.30) passes through chemical gaseous phase Deposition method deposits CVD graphene on cobalt particle surface, solves the lamella integrity issue of graphene, but CVD graphene makes With easily damaged in the process, intolerant to fretting wear.Chinese invention patent application (patent publication No. CN108154947A, application Day 2016.12.06) using graphene aqueous dispersion and water-absorbing resin as raw material, it is expanded, is done using water-absorbing resin water suction volume The characteristics of dry volume contraction, prepares graphene coated resin particle composite material.Although this method is using water-absorbing resin conduct Matrix increases the graphene adhesive force on surface using its swelling and the characteristics of contraction, it can be difficult to fundamentally improving graphene The performance of the adhesive force of lamella and entire compound particle.SCI document (Composites:Part A 84 (2016) 472-481, DOI:10.1016/j.compositesa.2016.02.027 covalent bond method) is used, by graphene oxide package to PI ball The lamella integrality on surface, graphene oxide itself is poor, tight although a large amount of oxygen-containing groups having can increase adhesive force Lamella electric conductivity is sacrificed again；By Covalent bonding together coated graphite alkene, coats thickness and clad ratio is also difficult to determine；Surface cladding Binding force be difficult to resist abrasion, clad is easy to fall off.SCI document (J.Mater.Chem.C, 2018,6,257) is by making Compounded mix is constructed by the graphene coated after reduction on nano copper particle surface with copper nano-particle redox graphene, But the binding force between graphene and copper is poor, graphene coated layer is not wear-resisting, and is easy to fall off.SCI document (Composites 144 (2017) 63e69 of Science and Technology) positively charged boron nitride is coated on negative by electrostatic attraction The PPS ball surface of electricity, and pass through the adhesive force of addition PEI and GA increase clad.But this method can not significantly increase The adhesive force of boron nitride, and preparation process is complicated.
Summary of the invention
The purpose of the present invention is to provide a kind of high conductivity and cost effective graphene Gradient Coated polyacrylic acid are multiple Close conducting particles preparation method, solve surface coating layer binding force in the prior art it is poor, it is not wear-resisting and be easy to fall off or The problems such as coating the electric conductivity for sacrificing conductive layer by covalent bond.
The technical scheme is that
A kind of preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated, the system of the composite conducting particles Standby process is, positively charged amination graphene is under the action of electrostatic attraction and concentration gradient, from aqueous dispersion liquid to swelling Electronegative polyacrylic acid core diffusion and absorption, along the surface of polyacrylic acid to core gradient distribution；It will gather later The pH value of the aqueous dispersions of acrylic particles and graphene is adjusted to 1~2, under this pH state, point of polyacrylic acid particle Subchain sudden contraction, by graphene lock between polyacrylic acid strand；Point to compound particle heating drying, to polyacrylic acid After subchain syneresis, graphene sheet layer is adsorbed and is lockked by the strand of polyacrylic acid, is firmly attached on polyacrylic acid grain The epidermis and core of son obtain the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The preparation method of the polyacrylic acid composite conducting particles of the graphene Gradient Coated, includes the following steps:
(1) graphene powder for expanding graft process preparation is distributed in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, oil bath is anti- After answering 6~10 hours, product is centrifuged and is washed, obtains carboxylated graphene；
(2) by the carboxylated graphene dispersion in n,N dimethylformamide DMF, 1- ethyl-(3- bis- is then added Dimethylaminopropyl) carbodiimide hydrochloride EDC, and ultrasonic disperse 0.5~2 hour, add ethylenediamine EDA, oil bath reaction 6 ~8 hours, product is centrifuged and is washed, amination graphene is obtained；
(3) amination graphene is dispersed in deionized water, and ultrasonic disperse 0.5~2 hour, is then added dry Dry polyacrylic acid particle, ultrasound 1~10 hour obtain the polyacrylic acid particle of swelling cladding；Dispersion liquid pH value is adjusted again To 1~2, shrink the strand of polyacrylic acid；Finally, the polyacrylic acid particle of the graphene Gradient Coated is taken out, set In 50~100 DEG C of baking oven, vacuum drying obtains the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The preparation method of the polyacrylic acid composite conducting particles of the graphene Gradient Coated, in step (1), expansion is inserted The graphene powder of layer method preparation, the atomic percent of oxygen element is less than 1%, and the lamella diameter of graphene powder is in 100nm Between~10 μm, the concentration of graphene powder is 1.2~5mg/ml.
The preparation method of the polyacrylic acid composite conducting particles of the graphene Gradient Coated, in step (1), the concentrated sulfuric acid Mass concentration be 60~80%, the mass concentration of concentrated nitric acid is 60~80%, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid be (2~ 4): 1.
The preparation method of the polyacrylic acid composite conducting particles of the graphene Gradient Coated, in step (1), carboxylated The atomic percent of oxygen element is 1%~15% in graphene, and the aqueous dispersions zeta potential value of carboxylated graphene is -35 ~-15mV, the lamella size of carboxylated graphene are 100nm~10 μm.
The preparation method of the polyacrylic acid composite conducting particles of the graphene Gradient Coated, in step (2), carboxylated The concentration of the DMF dispersion liquid of graphene is 1~5mg/ml, and the mass ratio of carboxylated graphene and EDC are 1:(2~10), EDA Additive amount be the corresponding 15~75mg carboxylated graphene of every 1ml EDA.
The preparation method of the polyacrylic acid composite conducting particles of the graphene Gradient Coated, in step (2), amination In graphene the atomic percent of nitrogen be 1%~8%, the atomic percent of oxygen element less than 7%, amination graphene Aqueous dispersions zeta potential value is 5~20mV, and the lamella size of amination graphene is 100nm~10 μm.
The preparation method of the polyacrylic acid composite conducting particles of the graphene Gradient Coated, in step (3), amination The concentration of graphene is 0.5~5mg/ml, and the mass ratio of polyacrylic acid particle and amination graphene is (12~100): 1.
The preparation method of the polyacrylic acid composite conducting particles of the graphene Gradient Coated, in step (3), polypropylene The partial size of acid particles is between 100nm~1mm.
The preparation method of the polyacrylic acid composite conducting particles of the graphene Gradient Coated, in step (3), graphene The polyacrylic acid composite conducting particles of Gradient Coated, graphene surface coating thickness are 1~100 μm, and surface coating rate is 100%, graphene thickness of diffusion layer is from the epidermis of polyacrylic acid composite conducting particles to core certain depth；Clad is wear-resisting Property for after ball milling in half an hour, surface coating layer is not fallen off.
Design philosophy of the invention is:
The present invention utilizes polypropylene under the premise of not sacrificing clad graphene sheet layer integrality and conductive and heat-conductive structure In acid molecule chain swelling process, ground gap and electronegativity between strand make positively charged graphene in concentration gradient and positive and negative Under the action of charge, it is diffused into the inside of polyacrylic acid particle.After the contraction of polyacrylic acid particle, graphene sheet layer gradient point Cloth is in the space of epidermis to core.It is acted on using the mechanical constraint of polyacrylic acid strand, graphene sheet layer is firmly locked Firmly.
Under the action of fretting wear, constraint and electrostatic attraction of the graphene sheet layer on surface due to strand, in conjunction with Power is stronger, can resist fretting wear.Even if the clad on surface is destroyed, being dispersed in the graphene sheet layer of core still can be with Conductive path is constituted, guarantees that the conductive and heat-conductive function of composite nanoparticle will not be destroyed.It is described multiple for different application demands The particle size and shape of condensation material are adjusted by partial size and the resin particle matrix of shape needed for selecting.This composite guide The preparation method of charged particle does not introduce other binders, while guaranteeing the lamella integrality of graphene, conductive layer and matrix Binding force is strong, and conductive layer clad ratio is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off；It is multiple Size and the electric conductivity for closing particle are controllable, good stability of the dimension；Good conductivity and production process is simple, production cost is low.
The invention has the advantages and beneficial effects that:
1, in the preparation method of graphene Gradient Coated polyacrylic acid composite conducting particles of the present invention, pass through amino graphite Alkene diffusion, core and the surface for embedding and being coated to polyacrylic acid particle, obtain graphene Gradient Coated polyacrylic acid composite guide Charged particle.
2, this composite conducting particles of the present invention, conductive layer and basal body binding force are strong, and conductive layer is wear-resisting and not easily to fall off. In the preparation method, by changing the concentration of amination graphene, the nitrogen element content of amination graphene, polyacrylic acid grain The partial size of son, the swelling time length of polyacrylic acid particle, the conditions such as mass ratio of graphene and polyacrylic acid particle, to poly- third Olefin(e) acid particle surface and internal graphene coated thickness and distribution are regulated and controled.This method arrives graphene sheet layer Gradient Coated On the core and surface of polyacrylic acid particle, due to taking Gradient Coated technique reinforced polypropylene acid molecule chain to graphene sheet layer Mechanical interlocking, enhance the adhesive force of graphene, avoid graphene coated layer poor adhesive force or due to enhancing its adhesive force The preparation drawback for sacrificing its performance, effectively avoids the problem of falling off.
3, the present invention guarantees the integrality and electric conductivity of graphene sheet layer during cladding, has very high clad ratio, And conductive layer clad ratio is high, cladding thickness, graphene depth of penetration are controllable, good stability of the dimension, the size of compound particle and Electric conductivity is controllable.
4, present invention introduces polyacrylic acid there is lesser density, it is and cheap, thus can further decrease and lead The density of electric filler, and can significantly reduce the dosage of graphene in conductive material, good conductivity and production process is simple are raw It produces at low cost.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of the graphene Gradient Coated polyacrylic acid composite conducting particles of an embodiment.
Fig. 2 is the scanned photograph of the surface topography of the polyacrylic acid composite conducting particles of graphene coated.Wherein, (a) is The surface coated scanning shape appearance figure of graphene coated polyacrylic acid particle under low power mode is (b) graphene under high power mode Coat the surface coated scanning shape appearance figure of polyacrylic acid particle.
Fig. 3 is the scanned photograph of the cross-section morphology of the polyacrylic acid composite conducting particles of graphene coated.Wherein, (a) is The profile scanning shape appearance figure of graphene coated polyacrylic acid particle under low power mode, it is (b) poly- for graphene coated under high power mode The profile scanning shape appearance figure of acrylic particles.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing Provide better embodiment of the invention.The above is only a preferred embodiment of the present invention, is not intended to limit patent of the invention Range, it is all using equivalent structure or equivalent process transformation made by description of the invention and accompanying drawing content, directly or It connects and is used in other related technical areas, be included within the scope of the present invention.
Unless otherwise defined, all technical and scientific terms used in the present invention and belong to technical field of the invention The normally understood meaning of technical staff it is identical.Used term is intended merely to retouch in the description of the invention in the present invention State the purpose of specific embodiment, it is not intended that in the limitation present invention.Term used in the present invention " and/or " it include one Or any and all combinations of multiple relevant listed items.
Referring to Fig. 1, the preparation method of the graphene Gradient Coated polyacrylic acid composite conducting particles of an embodiment, packet Include following steps:
The graphene powder for expanding graft process preparation is distributed in deionized water by S110, and the concentrated sulfuric acid and dense nitre is then added Acid is centrifuged and is washed after 50 DEG C of oil baths are reacted 6~10 hours, then by product, obtains the graphene of carboxylated.It is main Reaction equation is as follows:
Wherein, the graphene powder of expansion graft process preparation, the atomic percent of oxygen element is less than 1%, lamella diameter Between 100nm~10 μm.The concentration for expanding the graphene powder of graft process preparation is 1.2~5mg/ml.The quality of the concentrated sulfuric acid Concentration is 70%, and the mass concentration of concentrated nitric acid is 70%, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
In n,N dimethylformamide (DMF), 1- ethyl-is then added in the graphene dispersion of the carboxylated by S120 (3- dimethylaminopropyl) carbodiimide hydrochloride (EDC) simultaneously ultrasonic disperse 0.5~2 hour, ethylenediamine (EDA) is added, Oil bath is warming up to 50 DEG C and reacts 6~8 hours, then product is centrifuged and is washed, and obtains amidized graphene.It is main anti- Answer equation as follows:
Wherein, the atomic percent of the oxygen element of carboxylated graphene is 1%~15%, the water dispersion of carboxylated graphene Liquid zeta potential value is -35~-15mV, and lamella size is 100nm~10 μm.The concentration of the DMF dispersion liquid of carboxylated graphene For 1~5mg/ml, the mass ratio of carboxylated graphene and EDC are 1:10~1:2, and the additive amount of EDA is every 1ml ethylenediamine pair Answer 15~75mg carboxylated graphene.
S130 by the amidized graphene dispersion in deionized water, and ultrasonic disperse 0.5~2 hour, then plus Enter dry polyacrylic acid particle, ultrasound 1~10 hour obtains the polyacrylic acid particle of swelling cladding；Again by dispersion liquid pH value It is adjusted to 1~2, shrinks the strand of polyacrylic acid；Finally, the polyacrylic acid particle of the graphene Gradient Coated is taken Out, it is placed in 50~100 DEG C of baking oven, vacuum drying obtains the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The Gradient Coated refers to: there are concentration differences in water and in polyacrylic acid inside particles for amination graphene； Meanwhile positively charged amination graphene is attracted by the strand of electronegative polyacrylic acid, from the epidermis of polyacrylic acid particle Inwardly diffusion.Since the swelling rate of polyacrylic acid particle in water is different, the strand swelling time of superficial is early, strand Between space it is larger；The strand swelling time of core is late, and the space between strand is smaller.Graphene is in diffusion process In, it is most of to be diffused into certain depth from core.If polyacrylic acid strand complete swelling, graphene will diffuse into entire ball Internal portion, full of the gap between the strand from epidermis to core.After the strand syneresis of polyacrylic acid, graphene Lamella is fettered by strand, is firmly attached on epidermis and the inside of polyacrylic acid particle, obtains the poly- of graphene Gradient Coated Acrylic acid composite conducting particles.
Wherein, the atomic percent of the nitrogen of amination graphene is 1%~8%, and the atomic percent of oxygen element is small In 7%, the aqueous dispersions zeta potential value of amination graphene is 5~20mV, and lamella size is 100nm~10 μm.Amination The concentration of graphene is 0.5~5mg/ml, and the mass ratio of polyacrylic acid particle and amination graphene is (12~100): 1.It is poly- The partial size of acrylic particles is between 100nm~10 μm.
Graphene Gradient Coated polyacrylic acid composite conducting particles, are obtained by above-mentioned preparation method.In an embodiment In, the complex conductive particle of graphene Gradient Coated polyacrylic acid, surface layer graphene coated thickness degree can be controlled in 1~100 μ M, thickness of diffusion layer are from epidermis to entire core.
In above-mentioned preparation method, firstly, carboxylated processing is carried out to graphene powder using nitration mixture, in graphene film Layer edge carboxyl grafting functional group, generates active site；Then, functional group in situ is carried out to carboxylated graphene using ethylenediamine Substitution, in active site grafted amino group functional group；Later, polyacrylic acid particle is added, makes amination graphene in Electrostatic Absorption Under effect and concentration difference diffusion, diffusion is coated to surface and the core of polyacrylic acid particle；Dispersion liquid pH value is adjusted again To 1~2, shrink the strand of polyacrylic acid；Finally, the polyacrylic acid particle of the graphene Gradient Coated is taken out, set In 50~100 DEG C of baking oven, vacuum drying obtains the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The present invention is by changing the concentration of amination graphene, the nitrogen element content of amination graphene, polyacrylic acid grain The partial size of son, the swelling time length of polyacrylic acid particle, the conditions such as mass ratio of graphene and polyacrylic acid particle, to poly- third Olefin(e) acid particle surface and internal graphene coated thickness and distribution are regulated and controled.Graphene powder is coated to poly- third by this method On olefin(e) acid particle, not only solves the problems, such as that graphene powder is difficult to disperse in use in the base, ensure that graphene The integrality and electric conductivity of lamella, and there is very high clad ratio, and conductive layer clad ratio is high, cladding thickness, graphene seep It is controllable to enter depth, good stability of the dimension, the size and electric conductivity of compound particle be controllable.Simultaneously as taking Gradient Coated Technique is strapped in graphene in epidermis to the space of core by the strand of polyacrylic acid, enhances graphene sheet layer in matrix On adhesive force, effectively avoid the problem that falls off of conductive coating.In addition, the polyacrylic acid introduced has lesser density, and It is cheap, thus the density of conductive filler can be further decreased, and can significantly reduce graphene in conductive material Dosage, good conductivity and production process is simple, production cost is low.
Compared with silver powder, the complex conductive particle of this method preparation overcomes nano silver to be easy to happen electricity as conductive filler to move The problem of aoxidizing is moved and be easy to, effectively guarantees the chemical stability of conductive filler.Moreover, composite conductive powder prepared by the present invention Last apparent density is small, can be formed under lower packing ratio and arrive spot net, it is easier to dispersed in resin, nano silver is overcome to fill The unstable deficiency of conducting resinl electric conductivity, and can be with long-term preservation.
In the following, being further elaborated on by embodiment to the present invention.
Embodiment 1
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 1mm polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will be mixed It closes object ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The surface topography of graphene coated polyacrylic acid composite conducting particles obtained as shown in the scanned photograph in Fig. 2, As can be seen that graphene uniform is closely coated on the surface of polyacrylic resin from photo, between graphene sheet layer mutually Overlap joint forms conductive network.The cross-section morphology of material is as shown in the scanned photograph in Fig. 3, it can be seen that graphene sheet layer is gathered Acrylic resin is strapped between strand, and forms conductive network.Due to the pattern of other embodiments and the present embodiment sample It is close, behind repeat no more.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 50 μm, is expanded Layer is dissipated with a thickness of inside 100 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 2
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 1mm polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 100:1, will Mixture ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 50 μm, is expanded Layer is dissipated with a thickness of inside 60 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer clad ratio Height, cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 3
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 1mm polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 20:1, will be mixed It closes object ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 80 μm, is expanded Layer is dissipated with a thickness of inside 300 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 4
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 1mm polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will be mixed It closes object ultrasound 5 hours, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 50 μm, is expanded Layer is dissipated with a thickness of inside 200 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 5
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 1mm polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will be mixed It closes object ultrasound 10 hours, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 50 μm, is expanded Layer is dissipated with a thickness of inside 350 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 6
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 2mm polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will be mixed It closes object ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 50 μm, is expanded Layer is dissipated with a thickness of inside 60 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer clad ratio Height, cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 7
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 500 μm of polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will Mixture ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 70 μm, is expanded Layer is dissipated with a thickness of inside 120 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 8
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 200 μm of polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will Mixture ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 80 μm, is expanded Layer is dissipated with a thickness of from epidermis to entire core.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 9
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 50 μm of polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will Mixture ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 20 μm, is expanded Layer is dissipated with a thickness of from epidermis to entire core.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 10
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 3mg/ml is made.Then drying is added Partial size be 10 μm of polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will Mixture ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 5 μm, is expanded Layer is dissipated with a thickness of from epidermis to entire core.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 11
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 5mg/ml is made.Then drying is added Partial size be 1mm polyacrylic acid particle, the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will be mixed It closes object ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 80 μm, is expanded Layer is dissipated with a thickness of inside 150 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 12
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 150mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, ultrasound 1 hour, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid The volume of 3:1, the concentrated sulfuric acid and concentrated nitric acid is 40mL.
2. ultrasonic disperse liquid is placed in three-neck flask, the back flow reaction under constant temperature digital-display magnetic stirrer, reaction temperature 90 DEG C, the reaction time 7 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 8%, the aqueous dispersions zeta potential value of carboxylated graphene is -22mV, and the lamella size of carboxylated graphene is 3~5 μ m。
4. the concentration of carboxylated graphene is 3mg/ml by the carboxylated graphene dispersion in the DMF of 40ml, it is added The EDC of 300mg, ultrasonic agitation make its mixing be uniformly dispersed in 1 hour, dispersion liquid are placed in three-neck flask, the EDA of 2ml is instilled, It is heated under constant temperature digital-display magnetic stirrer, 50 DEG C of reaction temperature, the reaction time 5 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 2% in amination graphene, and the atomic percent of oxygen element is 6%, amino fossil The aqueous dispersions zeta potential value of black alkene is 10mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the dispersion liquid of 0.5mg/ml is made.Then it is added dry Dry partial size is the polyacrylic acid particle of 1mm, and the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, will Mixture ultrasound 1 hour, obtains the polyacrylic acid particle of swelling cladding.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 20 μm, is expanded Layer is dissipated with a thickness of inside 30 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer clad ratio Height, cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment 13
In the present embodiment, the polyacrylic acid composite conducting particles of graphene Gradient Coated the preparation method is as follows:
1. weighing expansion intercalated graphite alkene raw material 100mg, the atomic percent of oxygen element is 0.5% in graphene powder, Lamella diameter is 3~5 μm, is dissolved in nitration mixture, ultrasound 1 hour, and nitration mixture is that the concentrated sulfuric acid and concentrated nitric acid are mixed with volume ratio 3:1 The volume of solution, the concentrated sulfuric acid and concentrated nitric acid is 50mL.
2. preparation carboxylated graphene: ultrasonic disperse liquid being placed in three-neck flask, under constant temperature digital-display magnetic stirrer Back flow reaction, 90 DEG C of reaction temperature, the reaction time 10 hours.
3. reaction solution is poured into a large amount of deionized waters to terminate reaction, supernatant liquor is removed after standing a period of time, is remained Remaining mixed liquor filters filter membrane used and is the organic solvent filter membrane in 0.45 μm of aperture by vacuum filtration separation, and uses deionization Water clean repeatedly until pH of mixed for neutrality, obtain carboxylated graphene.The atomic percent of the oxygen element of carboxylated graphene Than being 12%, the aqueous dispersions zeta potential value of carboxylated graphene is -31mV, and the lamella size of carboxylated graphene is 3~5 μm。
4. by the carboxylated graphene dispersion in the n,N dimethylformamide of 60ml, the concentration of carboxylated graphene For 3mg/ml, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride 600mg is added, ultrasonic agitation makes it mixed for 1 hour Conjunction is uniformly dispersed, and dispersion liquid is placed in three-neck flask, instills 4ml ethylenediamine reagent, adds under constant temperature digital-display magnetic stirrer Heat, 70 DEG C of reaction temperature, the reaction time 8 hours.
5. finally separating mixed liquor by vacuum filtration and being cleaned repeatedly five times or more with deionized water, amination is obtained Graphene.The atomic percent of nitrogen is 5% in amination graphene, and the atomic percent of oxygen element is 7%, amino fossil The aqueous dispersions zeta potential value of black alkene is 18mV, and the lamella size of amination graphene is 3~5 μm.
6. the amination graphene is distributed in deionized water, the concentration of amination graphene is 3mg/ml, is added Dry partial size is the polyacrylic acid particle of 1mm, and the mass ratio of polyacrylic acid particle and the amination graphene is 50:1, By mixture ultrasound 1 hour, the polyacrylic acid particle of swelling cladding is obtained.
7. the pH value of dispersion liquid is adjusted to 1, in being stored at room temperature 1 hour, shrink the strand of polyacrylic acid particle, it will Graphene sheet layer is strapped in the epidermis and core of polyacrylic acid.
8. the polyacrylic acid particle of swelling cladding is taken out from dispersion liquid, it is placed in 80 DEG C of baking oven, is dried in vacuo To the polyacrylic acid composite conducting particles of graphene Gradient Coated.
The graphene surface coating thickness of the polyacrylic acid composite conducting particles of graphene Gradient Coated is 50 μm, is expanded Layer is dissipated with a thickness of inside 220 μm from epidermis.This composite conducting particles, conductive layer and basal body binding force are strong, conductive layer cladding Rate is high, and cladding thickness, graphene depth of penetration are controllable, and conductive layer is wear-resisting and not easily to fall off, and technical indicator is as follows:
Surface coating rate is 100%, and after compound particle mechanical ball mill half an hour, surface coating layer is still intact, does not have It falls off.
Embodiment described above only expresses several embodiments of the invention, and the description thereof is more specific and detailed, but not Limitations on the scope of the patent of the present invention therefore can be interpreted as.It should be pointed out that coming for those of ordinary skill in the art It says, under the premise of not departing from design of the invention, various modifications and improvements can be made, these belong to guarantor of the invention Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1. a kind of preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated, which is characterized in that the composite guide The preparation process of charged particle is that positively charged amination graphene is under the action of electrostatic attraction and concentration gradient, by water phase point Dispersion liquid is spread to the core of the electronegative polyacrylic acid of swelling and absorption, divides along the surface of polyacrylic acid to core gradient Cloth；The pH value of polyacrylic acid particle and the aqueous dispersions of graphene is adjusted to 1~2 later, under this pH state, polypropylene The strand sudden contraction of acid particles, by graphene lock between polyacrylic acid strand；To compound particle heating drying, to poly- After the strand syneresis of acrylic acid, graphene sheet layer is adsorbed and is lockked by the strand of polyacrylic acid, is firmly attached on The epidermis and core of polyacrylic acid particle obtain the polyacrylic acid composite conducting particles of graphene Gradient Coated.
2. the preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated according to claim 1, special Sign is, includes the following steps:
(1) graphene powder for expanding graft process preparation is distributed in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, oil bath reaction 6~ After 10 hours, product is centrifuged and is washed, obtains carboxylated graphene；
(2) by the carboxylated graphene dispersion in n,N dimethylformamide DMF, 1- ethyl-(3- dimethyl is then added Aminopropyl) carbodiimide hydrochloride EDC, and ultrasonic disperse 0.5~2 hour, add ethylenediamine EDA, oil bath reaction 6~8 Hour, product is centrifuged and is washed, amination graphene is obtained；
(3) amination graphene is dispersed in deionized water, and ultrasonic disperse 0.5~2 hour, drying is then added Polyacrylic acid particle, ultrasound 1~10 hour obtain the polyacrylic acid particle of swelling cladding；Dispersion liquid pH value is adjusted to 1 again~ 2, shrink the strand of polyacrylic acid；Finally, the polyacrylic acid particle of the graphene Gradient Coated is taken out, it is placed in 50~ In 100 DEG C of baking oven, vacuum drying obtains the polyacrylic acid composite conducting particles of graphene Gradient Coated.
3. the preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated according to claim 2, special Sign is, in step (1), the graphene powder of expansion graft process preparation, the atomic percent of oxygen element is less than 1%, graphite For the lamella diameter of alkene powder between 100nm~10 μm, the concentration of graphene powder is 1.2~5mg/ml.
4. the preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated according to claim 2, special Sign is, in step (1), the mass concentration of the concentrated sulfuric acid is 60~80%, and the mass concentration of concentrated nitric acid is 60~80%, the concentrated sulfuric acid Volume ratio with concentrated nitric acid is (2~4): 1.
5. the preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated according to claim 2, special Sign is, in step (1), the atomic percent of oxygen element is 1%~15% in carboxylated graphene, the water of carboxylated graphene Dispersion liquid zeta potential value is -35~-15mV, and the lamella size of carboxylated graphene is 100nm~10 μm.
6. the preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated according to claim 2, special Sign is, in step (2), the concentration of the DMF dispersion liquid of carboxylated graphene is 1~5mg/ml, carboxylated graphene and EDC's Mass ratio is 1:(2~10), the additive amount of EDA is the corresponding 15~75mg carboxylated graphene of every 1ml EDA.
7. the preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated according to claim 2, special Sign is, in step (2), the atomic percent of nitrogen is 1%~8% in amination graphene, the atomic percent of oxygen element Than less than 7%, the aqueous dispersions zeta potential value of amination graphene is 5~20mV, and the lamella size of amination graphene is 100nm~10 μm.
8. the preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated according to claim 2, special Sign is, in step (3), the concentration of amination graphene is 0.5~5mg/ml, polyacrylic acid particle and amination graphene Mass ratio is (12~100): 1.
9. the preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated according to claim 2, special Sign is that in step (3), the partial size of polyacrylic acid particle is between 100nm~1mm.
10. the preparation method of the polyacrylic acid composite conducting particles of graphene Gradient Coated according to claim 2, special Sign is, in step (3), the polyacrylic acid composite conducting particles of graphene Gradient Coated, and graphene surface coating thickness Be 1~100 μm, surface coating rate 100%, graphene thickness of diffusion layer be from the epidermises of polyacrylic acid composite conducting particles to Core certain depth；Clad wearability is after ball milling in half an hour, and surface coating layer is not fallen off.
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