CN106745237A - A kind of layer type casting moulding Graphene non-metallic metal composite and preparation method - Google Patents

A kind of layer type casting moulding Graphene non-metallic metal composite and preparation method Download PDF

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CN106745237A
CN106745237A CN201611256383.4A CN201611256383A CN106745237A CN 106745237 A CN106745237 A CN 106745237A CN 201611256383 A CN201611256383 A CN 201611256383A CN 106745237 A CN106745237 A CN 106745237A
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oxide
graphene
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张文娟
尹宗杰
楚双印
李芳�
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00Compounds of zirconium
    • C01G25/02Oxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/04Oxides; Hydroxides
    • C01G23/047Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/80Particles consisting of a mixture of two or more inorganic phases

Abstract

The present invention relates to a kind of layer type casting moulding Graphene non-metallic metal composite and preparation method thereof.The preparation method of layer type casting moulding Graphene non-metallic metal composite, graphene quantum dot and/or microplate are carried out into mixed grinding, shearing with non-metallic metal material under ultrasonication, quenching carried out through laser treatment, refined, promote molecular rearrangement, grafting fusion after drying.Layer type casting moulding Graphene non-metallic metal composite prepared by the invention, it is low with high rigidity, high intensity, resistivity, the superior function for using easily is processed, can be widely applied to the material processing fields such as dental implant, super electric drill;Battery, ultracapacitor energy storage Material Field;Catalyst material field;Heat sink material field;Medical domain;Coating material field;Electrically conductive ink;Photoelectricity, sensor material field;Biological association area etc..

Description

A kind of layer type casting moulding Graphene-nonmetallic-metallic composite and preparation method
Technical field
The present invention relates to Graphene applied technical field, more particularly to a kind of layer type casting moulding Graphene-nonmetallic-metal is multiple Condensation material and preparation method.
Background technology
Single-layer graphene film is made up of one layer of intensive carbon hexatomic ring, does not have any fault of construction, and its thickness is 0.35nm or so, is two-dimensional nano-carbon material most thin so far.Meanwhile, it be also constitute other carbon group materials it is substantially single Unit, can obtain that the fullerene of zero dimension, curling obtain one-dimensional CNT and stacking obtains the graphite of three-dimensional by warpage.Stone Repetition period unit most basic in black alkene is the most stable phenyl ring knot ditch in organic chemistry, it be it is current untill best two Dimension nano material.The Graphene prepared in reality does not only exist individual layer, also there is multilayer.Due to its unique structure, Graphene Various types of properties it is also very excellent.It is most thin most light material in the world, and thickness is most thin up to 0.34nm, and specific surface area is 2630m2/g, carrier mobility at room temperature is about 200,000 (cm2/ vs), oneself knows one of intensity highest material, compares diamond It is also hard, taller upper 100 times of strength ratio steel best in the world.It possesses good toughness again simultaneously, and can bend, The theoretical Young's modulus of ideal graphite alkene reaches 1.0TPa, and fracture strength is 130GPa.Thermal conductivity factor is up to 5000W/mK, is current Untill highest.
At present, domestic and international researcher being combined in grapheme material, modification application aspect has carried out more research, as in State's number of patent application:CN201610528611.2, disclose a kind of porous carbon-Graphene-metal oxide composite material and its Preparation method and application.The method has the material of porous material in nature by finding, then with graphene oxide by height Temperature is thermally treated resulting in porous carbon-graphene composite material, then metal oxide is compound on above-mentioned composite, obtains one kind Porous carbon-Graphene-metal oxide composite material.The material can solve manually to prepare porous material specific surface area with structure not Continuously, the larger contradictory problems of internal resistance, and porous material specific surface area and electrical conductivity are further improved using grapheme material, make Obtain high-specific surface area and high conductivity is unified on same composite.Chinese Patent Application No.: CN201610481436.6, invents a kind of organic metal framework/nano-stannic oxide/Graphene composite photocatalyst material and its system Preparation Method and purposes, composite are that, for carrier, nano-stannic oxide is scattered in organic metal framework (Zr-MOFs, UiO66) The organic metal framework surface, Graphene is then wrapped in the organic metal framework with nano-stannic oxide, shows higher Catalysis activity.Chinese Patent Application No.:CN201610452943.7, discloses a kind of lead comprising slicker solder-rare earth-Graphene The preparation method of accumulator plate grid alloy, by adding rare earth element, significantly improves crystal grain, the grain boundary features of alloy, crystal grain chi Very little to be substantially reduced, grain boundary area increase under same current density, can substantially reduce etching extent.Chinese Patent Application No.: CN201610825355.3 discloses a kind of preparation method of nickel oxide/graphene oxide composite material, and it is existing in order to solve Prepare that metal oxide particle in metal oxide/graphene composite material is big and particle diameter is uneven and specific capacitance is relatively low Problem.Chinese Patent Application No.:CN201610821003.0, discloses a kind of iron oxyhydroxide/graphenoxide oxide composite material Preparation method and applications.Iron oxyhydroxide/graphenoxide oxide composite material is by the suspension and hydroxyl of graphene oxide The suspension of iron oxide is according to volume ratio 1:It is composited by hydro-thermal method after 1~2 mixing, dispersion.Chinese Patent Application No.: CN201610804294.2, discloses a kind of preparation method of LiFePO4/graphene composite material.The method mainly includes will Waste lithium iron phosphate battery positive plate is mixed by organic solvent immersion, ultrasonication, ball milling, roasting, quenching and conductive black Close roasting and obtain LiFePO 4 material;Then natural flake graphite and sodium nitrate are added in sulfuric acid solution, by permanganic acid The oxidation such as potassium obtains graphene oxide;LiFePO 4 material and the graphene oxide mixing that will finally obtain, with N- methyl -2- pyrroles Pyrrolidone is dispersant, and ball milling obtains final product LiFePO4/graphene composite material.Chinese Patent Application No.: CN201610768001.X, discloses a kind of preparation method of stannic disulfide/graphene nanocomposite material, lithium ion battery and bears Pole, lithium ion battery, preparation method step include hydro-thermal operation, compound working procedure, and preparation method of the present invention causes that stannic disulfide exists Graphenic surface directly carries out growth in situ, by washing, dries and obtains sheet stannic disulfide/graphene composite material, the material Material is applied to lithium ion battery negative material, effectively improves the stability and electric conductivity of material, lifts battery performance, has Good cycling stability, the advantages of specific energy density is high.Chinese Patent Application No.:CN201610763257.1, discloses a kind of three Preparation method, lithium ion battery negative, the lithium ion battery of two iron/graphene composite material are aoxidized, preparation method step includes Hydro-thermal operation, compound working procedure, preparation method of the present invention cause di-iron trioxide nano particle uniform load in three-dimensional grapheme In surface and pore passage structure, by washing, dry obtain sesquioxide/graphene composite material, the materials application in lithium from Sub- battery, with high power capacity, have extended cycle life, low cost and easily large-scale production etc. excellent properties.Chinese Patent Application No.: CN201610764913.X, discloses a kind of preparation method of manganese sulfide/graphene nanocomposite material, lithium ion battery and bears Pole, lithium ion battery, preparation method step include hydro-thermal operation, compound working procedure, and preparation method of the present invention causes manganese sulfide in stone Black alkene surface directly carries out growth in situ, by washing, dries and obtains manganese sulfide/graphene composite material, and the present invention passes through sulphur Change manganese and three-dimensional redox graphene is combined the shortcomings of to overcome stability difference caused by its Volume Changes, strengthen its conductive Property, so as to improve the performance of lithium ion battery, the materials application has good cycling stability in lithium ion battery negative material, The advantages of specific energy density is high.Chinese Patent Application No.:CN201610748848.1, is related to a kind of with level porous hollow Molybdenum bisuphide/the graphene composite material and its synthetic method of microspheroidal structure, belong to Micron-nano composites and prepare and synthesis Technical field.Filled with big specific capacitance and excellent circulation when the composite is used as electrode material for super capacitor Discharge stability, illustrates wide application prospect.Chinese Patent Application No.:CN201610594377.3, discloses one kind The preparation method of the fluorinated graphene composite of Nano Silver is loaded with, the composite for obtaining has premium properties.It is Chinese special Sharp application number:A kind of manganese cobalt sulfide/graphene composite material preparation technology of electrochemical performance, electricity in the preparation technology Chemical deposition uses three-electrode system, and working electrode is three-dimensional graphene foam, is platinized platinum to electrode, and reference electrode is Ag/ AgCl normal electrodes.This technological operation is easy, the structure of matter stabilization of preparation, and changing parameter can change the pattern of material, enter And the chemical property of material is lifted, can be used for large area and prepare electrode material.
In sum, although Graphene and its composite and technology are applied to more multi-field, and performance improvement is obtained And lifting, but the Graphene with hard high-strength due to interfacial energy it is high, intermolecular active force and chemical bond are made With by force and be necessarily susceptible to reunite.Therefore, due to there is lamination and reunion when graphene composite material is prepared into, no The performance advantage of high rigidity, high intensity and the high heat conduction of grapheme material can be fully demonstrated, this problem limits it bigger Scope, the application in broader field.
The content of the invention
Present invention aim to address the deficiencies in the prior art, there is provided a kind of layer type casting moulding Graphene-nonmetallic-metal is multiple The preparation method of condensation material.The present invention is opened between graphene sheet layer under ultrasonication, the Graphene material under laser action Material is merged with nonmetallic-metallics, and the material for obtaining has high rigidity, high intensity, resistivity low, is easily processed and is used Superior function, can be widely applied to the material processing fields such as dental implant, super electric drill;Battery, ultracapacitor energy storage material Material field;Catalyst material field;Heat sink material field;Medical domain;Coating material field;Electrically conductive ink;Photoelectricity, sensor Material Field;Biological association area etc..
The present invention is achieved by the following technical solutions:
The preparation method of layer type casting moulding Graphene-nonmetallic-metallic composite, it is characterised in that comprise the following steps:
(1) by graphene quantum dot and/or graphene microchip and non-metal simple-substance/compound-metal under ultrasonication Simple substance/compound carries out mixed grinding, shearing, and composite slurry material or composite powder material is obtained;
(2) obtained composite slurry material or powder body material are dried, obtain anhydrous composite powder material;
(3) obtained anhydrous composite powder material carried out into quenching through laser treatment, refined, promote molecular rearrangement, grafting Fusion, obtains a layer type casting moulding Graphene-nonmetallic-metallic composite.
Further, the metal simple-substance be zirconium, titanium, lead, nickel, copper, silver, molybdenum, gold, palladium, zinc, aluminium, iron, cobalt, chromium, manganese, One or more in tin, iridium, ruthenium, indium, lanthanide series metal simple substance.
Further, the non-metal simple-substance is in sulphur, nitrogen, silicon, phosphorus, boron, fluorine, chlorine, arsenic, selenium, bromine, tellurium, iodine, astatine Plant or several.
Further, the metallic compound is zirconium oxide, molybdenum bisuphide, tungsten disulfide, lead oxide, vulcanized lead, hydrogen-oxygen Change nickel, nickel oxide, nickel phosphide, cupric oxide, silver oxide, palladium bichloride, zinc oxide, aluminum oxide, iron oxide, iron phosphide, cobalt sulfide, sulphur Lead plumbate, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium, vanadium phosphate sodium, lithium ferric manganese phosphate, manganese silicate of lithium, ferric metasilicate lithium, lithium titanate, Cobalt acid lithium, LiMn2O4, nickel ion doped, nickle cobalt lithium manganate, cobalt oxide, titanium oxide, titanium boride, vanadium oxide, cadmium hydroxide, vulcanization Cadmium, chromium oxide, manganese oxide, tin oxide, antimony oxide, tungsten oxide, bismuth oxide, yittrium oxide, zirconium oxide, zirconium silicate, yttrium oxide, chlorination Iridium, iridium complex, silver oxide, ruthenium-oxide, ruthenic acid are secret, one or more in ruthenic acid lead, scandium oxide, indium oxide, magnesia.
Further, the nonmetallic compound is boron nitride, CNT, carbon fiber, polyaniline, rare earth, rubber, modeling One or more of material, polypyrrole, polythiophene, resin cation, resin anion (R.A.).
Further, the ultrasonication is produced by ultrasonic head, ultrasonic device or Vltrasonic device.
Preferably, the mixed grinding of step (1) is carried out under elevated pressure conditions, and pressure is 10-250MPa, and the time is 10- 60min.Solid phase mixing grinding shearing under condition of high voltage, not only causes mixture dispersion, mixing evenly, improves its dispersion mixed The uniformity of conjunction, more effectively reaches the stacking and reunion for preventing graphene quantum dot and/or graphene microchip, beneficial to Graphene With the compound action and enhancing adhesion of metallics.
Further, the mixed grinding of step (1) uses the one kind or two in high pressure liquid stream method or physical grinding method Plant combination.Wherein, the high pressure liquid stream method, refers to mixture to be ground through high-pressure fluid, is sheared, and is crushed, mixed Method, wherein fluid is water, ethanol, acetone, formamide, 1-METHYLPYRROLIDONE, acetonitrile, methyl alcohol, propyl alcohol, acetone, dioxy Six rings, tetrahydrofuran, MEK, n-butanol, ethyl acetate, ether, isopropyl ether, dichloromethane, chloroform, bromoethane, benzene, tetrachloro Change carbon, carbon disulfide, hexamethylene, hexane, one or more in kerosene.Temperature during high pressure liquid stream method mixed grinding is 2-18 DEG C, it is preferable that temperature is 4-6 DEG C.Brownian movement violent when can prevent high temperature is produced reunites again.
The physical grinding method, refers to mixture to be ground through high pressure solid, is sheared, the side for crushed, mixing Method.
Further, the drying means of step (2) is atmosphere pressure desiccation, low pressure seasoning, boulton process, supercritical drying Dry method or spray drying process.
The present invention also provides a kind of layer type casting moulding Graphene-nonmetallic-metallic composite, it is characterised in that by above-mentioned Preparation method obtain.
The beneficial effects of the invention are as follows:
By preparation method of the invention so that avoid lamination and reunion during Graphene application, and prepared by the present invention Layer type casting moulding Graphene answers-nonmetallic-metallic compound composite, is beaten between graphene sheet layer under ultrasonication Open, grapheme material is merged with nonmetallic-metallic compound under laser action, the material for obtaining has high rigidity, height Intensity, resistivity are low, are easily processed the superior function for using, and can be widely applied to the processing of the materials such as dental implant, super electric drill Field;Battery, ultracapacitor energy storage Material Field;Catalyst material field;Heat sink material field;Medical domain;Coating material Material field;Electrically conductive ink;Photoelectricity, sensor material field;Biological association area etc..
Specific embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
The layer type casting moulding Graphene-nonmetallic-metallic composite of the present embodiment, its preparation method comprises the following steps:
(1) graphene quantum dot, Zirconium oxide powder, rare earth are mixed under ultrasonic probe effect, it is high using pure water Pressure liquid flow method high pressure abrasive, shearing, pressure are 220MPa, and the time is 35min, and temperature is 2 DEG C, and composite slurry material is obtained;
(2) obtained composite slurry material is vacuum dried, pressure is 200Pa, drying time is 60min, is obtained Anhydrous composite powder material;
(3) by drying after anhydrous composite powder material through laser treatment carry out quenching, refine, promote molecular rearrangement, connect Branch fusion, obtains a layer type casting moulding Graphene-nonmetallic-metallic composite.
In other embodiments, graphene quantum dot can also use graphene microchip or graphene quantum dot and Graphene The mixture of microplate replaces;Vacuum drying pressure can be in 50-200Pa scopes, and drying time is 20-60min.
Embodiment 2
The layer type casting moulding Graphene-nonmetallic-metallic composite of the present embodiment, its preparation method comprises the following steps:
(1) graphene microchip is mixed with titania powder, polyaniline under ultrasound reactor effect, is used Ethanol high pressure liquid stream method high pressure abrasive, shearing, pressure are 180MPa, and the time is 45min, and temperature is 18 DEG C, and composite slurry is obtained Material;
(2) obtained composite slurry material is vacuum dried, pressure is 50Pa, drying time is 20min, obtains nothing Water composite powder material;
(3) by drying after anhydrous composite powder material carry out quenching of laser, refine, promote molecular rearrangement, grafting fusion, Obtain a layer type casting moulding Graphene-nonmetallic-metallic composite.
In other embodiments, titania powder can also use zirconium oxide, molybdenum bisuphide, tungsten disulfide, lead oxide, sulphur Change lead, nickel hydroxide, nickel oxide, nickel phosphide, cupric oxide, silver oxide, palladium bichloride, zinc oxide, aluminum oxide, iron oxide, iron phosphide, Cobalt sulfide, lead sulfate, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium, vanadium phosphate sodium, lithium ferric manganese phosphate, manganese silicate of lithium, ferrosilite Lithium, lithium titanate, cobalt acid lithium, LiMn2O4, nickel ion doped, nickle cobalt lithium manganate, cobalt oxide, titanium boride, vanadium oxide, cadmium hydroxide, sulphur Cadmium, chromium oxide, manganese oxide, tin oxide, antimony oxide, tungsten oxide, bismuth oxide, yittrium oxide, zirconium oxide, zirconium silicate, yttrium oxide, chlorine Change iridium, iridium complex, silver oxide, ruthenium-oxide, secret ruthenic acid, ruthenic acid lead, scandium oxide, indium oxide, one or more in magnesia Instead of;Polyaniline can also use boron nitride, CNT, carbon fiber, rare earth, rubber, plastics, polypyrrole, polythiophene, cation One or more replacements of resin, resin anion (R.A.).
Embodiment 3
The layer type casting moulding Graphene-nonmetallic-metallic composite of the present embodiment, its preparation method comprises the following steps:
(1) graphene microchip, titania powder, rare earth are mixed under ultrasonic probe effect, is ground using physics Mill method high pressure abrasive, shearing, pressure is 180MPa, and the time is 45min, and composite slurry material is obtained;
(2) obtained composite slurry material is carried out into constant pressure and dry, drying time is 30-300min, obtains anhydrous compound Powder body material;
(3) by drying after anhydrous composite powder material carry out quenching of laser, refine, promote molecular rearrangement, grafting fusion, Obtain a layer type casting moulding Graphene-nonmetallic-metallic composite.
Embodiment 4
The layer type casting moulding Graphene-nonmetallic-metallic composite of the present embodiment, its preparation method comprises the following steps:
(1) graphene microchip is mixed with zirconium, sulphur under ultrasonic probe effect, is ground using physical grinding method high pressure Mill, shearing, pressure is 10MPa, and the time is 60min, and composite slurry material is obtained;
(2) obtained composite slurry material is spray-dried, drying time is 30-200min, is obtained anhydrous compound Powder body material;
(3) by drying after anhydrous composite powder material carry out quenching of laser, refine, promote molecular rearrangement, grafting fusion, Obtain a layer type casting moulding Graphene-nonmetallic-metallic composite.
In other embodiments, zirconium can also by titanium, lead, nickel, copper, silver, molybdenum, gold, palladium, zinc, aluminium, iron, cobalt, chromium, manganese, One or more replacements in tin, iridium, ruthenium, indium, lanthanide series metal simple substance;Sulphur can also by nitrogen, silicon, phosphorus, boron, fluorine, chlorine, arsenic, selenium, One or more replacements in bromine, tellurium, iodine, astatine.
Embodiment 5
The layer type casting moulding Graphene-nonmetallic-metallic composite of the present embodiment, its preparation method comprises the following steps:
(1) graphene quantum dot is mixed with silicon, Zinc oxide powder under ultrasonic probe effect, using physical grinding Method high pressure abrasive, shearing, pressure is 250MPa, and the time is 10min, and composite powder material is obtained;
(2) obtained composite slurry material is carried out into supercritical drying, pressure is 500Pa, and drying time is 100min, is obtained To anhydrous composite powder material;
(3) by drying after anhydrous composite powder material carry out quenching of laser, refine, promote molecular rearrangement, grafting fusion, Obtain a layer type casting moulding Graphene-nonmetallic-metallic composite.
In other embodiments, silicon can also be by the one kind in sulphur, nitrogen, phosphorus, boron, fluorine, chlorine, arsenic, selenium, bromine, tellurium, iodine, astatine Or several replacements;Zinc oxide powder can also by zirconium oxide, molybdenum bisuphide, tungsten disulfide, lead oxide, vulcanized lead, nickel hydroxide, Nickel oxide, nickel phosphide, cupric oxide, silver oxide, palladium bichloride, zinc oxide, aluminum oxide, iron oxide, iron phosphide, cobalt sulfide, lead sulfate, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium, vanadium phosphate sodium, lithium ferric manganese phosphate, manganese silicate of lithium, ferric metasilicate lithium, lithium titanate, cobalt acid Lithium, LiMn2O4, nickel ion doped, nickle cobalt lithium manganate, cobalt oxide, titanium oxide, titanium boride, vanadium oxide, cadmium hydroxide, cadmium sulfide, oxygen Change chromium, manganese oxide, tin oxide, antimony oxide, tungsten oxide, bismuth oxide, yittrium oxide, zirconium oxide, zirconium silicate, yttrium oxide, iridium chloride, iridium Complex compound, silver oxide, ruthenium-oxide, ruthenic acid are secret, one or more replacements in ruthenic acid lead, scandium oxide, indium oxide, magnesia;It is super Critical dry pressure can be in the range of 10-1000Pa, and drying time is 15-200min.
The invention is not limited in above-mentioned implementation method, if not departing from the present invention to various changes of the invention or deformation Spirit and scope, if these are changed and within the scope of deformation belongs to claim of the invention and equivalent technologies, then this hair It is bright to be also intended to comprising these changes and deform.

Claims (10)

1. the preparation method of layer type casting moulding Graphene-nonmetallic-metallic composite, it is characterised in that comprise the following steps:
(1) under ultrasonication by graphene quantum dot and/or graphene microchip and non-metal simple-substance/compound-metal simple-substance/ Compound carries out mixed grinding, shearing, and composite slurry material or composite powder material is obtained;
(2) obtained composite slurry material or powder body material are dried, obtain anhydrous composite powder material;
(3) obtained anhydrous composite powder material carried out into quenching through laser treatment, refined, promote molecular rearrangement, grafting fusion, Obtain layer type casting moulding Graphene-nonmetallic-metallic composite.
2. the according to claim 1 layer of preparation method of type casting moulding Graphene-nonmetallic-metallic composite, its feature It is:The metal simple-substance be zirconium, titanium, lead, nickel, copper, silver, molybdenum, gold, palladium, zinc, aluminium, iron, cobalt, chromium, manganese, tin, iridium, ruthenium, indium, One or more in lanthanide series metal simple substance.
3. the according to claim 1 layer of preparation method of type casting moulding Graphene-nonmetallic-metallic composite, its feature It is:The non-metal simple-substance is one or more in sulphur, nitrogen, silicon, phosphorus, boron, fluorine, chlorine, arsenic, selenium, bromine, tellurium, iodine, astatine.
4. the according to claim 1 layer of preparation method of type casting moulding Graphene-nonmetallic-metallic composite, its feature It is:The metallic compound be zirconium oxide, molybdenum bisuphide, tungsten disulfide, lead oxide, vulcanized lead, nickel hydroxide, nickel oxide, Nickel phosphide, cupric oxide, silver oxide, palladium bichloride, zinc oxide, aluminum oxide, iron oxide, iron phosphide, cobalt sulfide, lead sulfate, ferric phosphate Lithium, lithium manganese phosphate, phosphoric acid vanadium lithium, vanadium phosphate sodium, lithium ferric manganese phosphate, manganese silicate of lithium, ferric metasilicate lithium, lithium titanate, cobalt acid lithium, mangaic acid Lithium, nickel ion doped, nickle cobalt lithium manganate, cobalt oxide, titanium oxide, titanium boride, vanadium oxide, cadmium hydroxide, cadmium sulfide, chromium oxide, oxygen Change manganese, tin oxide, antimony oxide, tungsten oxide, bismuth oxide, yittrium oxide, zirconium oxide, zirconium silicate, yttrium oxide, iridium chloride, iridium complex, Silver oxide, ruthenium-oxide, ruthenic acid are secret, one or more in ruthenic acid lead, scandium oxide, indium oxide, magnesia.
5. the according to claim 1 layer of preparation method of type casting moulding Graphene-nonmetallic-metallic composite, its feature It is:The nonmetallic compound is boron nitride, CNT, carbon fiber, polyaniline, rare earth, rubber, plastics, polypyrrole, poly- One or more of thiophene, resin cation, resin anion (R.A.).
6. the according to claim 1 layer of preparation method of type casting moulding Graphene-nonmetallic-metallic composite, its feature It is:The ultrasonication is produced by ultrasonic head, ultrasonic device or Vltrasonic device.
7. the according to claim 1 layer of preparation method of type casting moulding Graphene-nonmetallic-metallic composite, its feature It is:The mixed grinding of step (1) is carried out under elevated pressure conditions, and pressure is 10-250MPa, and the time is 10-60min.
8. the according to claim 1 layer of preparation method of type casting moulding Graphene-nonmetallic-metallic composite, its feature It is:The mixed grinding of step (1) uses one or two combinations in high pressure liquid stream method or physical grinding method.
9. the according to claim 1 layer of preparation method of type casting moulding Graphene-nonmetallic-metallic composite, its feature It is:The drying means of step (2) is that atmosphere pressure desiccation, low pressure seasoning, boulton process, supercritical drying or spraying are dry Dry method.
10. a kind of layer type casting moulding Graphene-nonmetallic-metallic composite, it is characterised in that by any institute of claim 1~9 The preparation method stated is obtained.
CN201611256383.4A 2016-12-30 2016-12-30 A kind of layer type casting moulding Graphene non-metallic metal composite and preparation method Pending CN106745237A (en)

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CN111650261A (en) * 2020-06-09 2020-09-11 苏州科技大学 Conductive ink for electrochemical biosensor and preparation method and application thereof
CN113096885A (en) * 2021-04-07 2021-07-09 宁波龙圣新材料科技有限公司 Preparation method of low-resistance high-transparency conductive film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844761A (en) * 2010-05-28 2010-09-29 上海师范大学 Method of adopting laser radiation for preparing reduction-oxidation graphene
CN104174856A (en) * 2014-08-29 2014-12-03 中国科学院重庆绿色智能技术研究院 Method for preparing TiAl-based composite powder material
CN104403343A (en) * 2014-05-31 2015-03-11 福州大学 Preparation method of solution for 3D printing of carbon nano-tube film or graphene film
CN106046755A (en) * 2016-07-29 2016-10-26 佛山市高明区诚睿基科技有限公司 Polyurethane composite material for 3D (three-dimensional) printing

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844761A (en) * 2010-05-28 2010-09-29 上海师范大学 Method of adopting laser radiation for preparing reduction-oxidation graphene
CN104403343A (en) * 2014-05-31 2015-03-11 福州大学 Preparation method of solution for 3D printing of carbon nano-tube film or graphene film
CN104174856A (en) * 2014-08-29 2014-12-03 中国科学院重庆绿色智能技术研究院 Method for preparing TiAl-based composite powder material
CN106046755A (en) * 2016-07-29 2016-10-26 佛山市高明区诚睿基科技有限公司 Polyurethane composite material for 3D (three-dimensional) printing

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUE JIANG ET AL.: ""Versatile graphene oxide putty-like material"", 《ADVANCED MATERIALS》 *

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* Cited by examiner, † Cited by third party
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CN107501646B (en) * 2017-09-06 2019-10-15 北京化工大学 Graphene quantum dot/rubber nano composite material preparation method
CN107501646A (en) * 2017-09-06 2017-12-22 北京化工大学 The preparation method of graphene quantum dot/rubber nano composite material
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CN109868117A (en) * 2017-12-02 2019-06-11 宜兴市乐华冶金辅助材料有限公司 A kind of high-performance fin material
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CN108543109A (en) * 2018-03-13 2018-09-18 淮阴工学院 It is low to grind dual antibacterial titanium-based nano composite material bone implant and its manufacturing process
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CN110289176A (en) * 2019-02-25 2019-09-27 常州大学 A kind of preparation method for the polyaniline grafted redox graphene/multi-wall carbon nano-tube composite material can be used for electrochemical energy storage
CN110514603A (en) * 2019-09-24 2019-11-29 广西民族师范学院 Optical electro-chemistry sensor and its preparation method and application for detecting kanamycins
CN110514603B (en) * 2019-09-24 2021-10-26 广西民族师范学院 Photoelectrochemical sensor for detecting kanamycin and preparation method and application thereof
CN111468141A (en) * 2019-11-21 2020-07-31 中山大学 Preparation method and application of two-dimensional amorphous-crystalline heterojunction
CN111468141B (en) * 2019-11-21 2021-08-13 中山大学 Preparation method and application of two-dimensional amorphous-crystalline heterojunction
CN111584247A (en) * 2020-05-20 2020-08-25 璧靛悍 V-shaped groove2O5Nitrogen-sulfur-loaded double-doped porous carbon supercapacitor electrode material and preparation method thereof
CN111584247B (en) * 2020-05-20 2021-11-05 重庆普朗电气设备有限公司 V-shaped groove2O5Nitrogen-sulfur-loaded double-doped porous carbon supercapacitor electrode material and preparation method thereof
CN111650261A (en) * 2020-06-09 2020-09-11 苏州科技大学 Conductive ink for electrochemical biosensor and preparation method and application thereof
CN113096885A (en) * 2021-04-07 2021-07-09 宁波龙圣新材料科技有限公司 Preparation method of low-resistance high-transparency conductive film
CN113096885B (en) * 2021-04-07 2022-09-09 佳雅(威海)新材料科技有限公司 Preparation method of low-resistance high-transparency conductive film

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Application publication date: 20170531