CN106670476A - Graphene-nonmetal-metal composite material for 3D printing, preparation method and application - Google Patents
Graphene-nonmetal-metal composite material for 3D printing, preparation method and application Download PDFInfo
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- CN106670476A CN106670476A CN201611258221.4A CN201611258221A CN106670476A CN 106670476 A CN106670476 A CN 106670476A CN 201611258221 A CN201611258221 A CN 201611258221A CN 106670476 A CN106670476 A CN 106670476A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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Abstract
The invention relates to a graphene-nonmetal-metal composite material for 3D printing, a preparation method and application. The preparation method comprises the following steps: (1) mixing, grinding and shearing graphene quantum dots and/or graphene micro-sheets, nonmetal simple substances and/or nonmetal compounds, and metal simple substances and/or metal compounds under the effect of ultrasonic waves (the frequency of the ultrasonic waves is 10-100 KHz) to obtain a composite slurry material or a composite powder material, wherein the mass ratio of the graphene quantum dots and/or the graphene micro-sheets, the nonmetal simple substances and/or the nonmetal compounds, and the metal simple substances and/or the metal compounds is 1: (1-45): (1-45); and (2) drying the prepared composite slurry material or powder material. The invention provides the laser sintering graphene-nonmetal-metal composite material for 3D printing and the preparation method of the laser sintering graphene-nonmetal-metal composite material. The composite material has excellent properties of high hardness, high strength, corrosion resistance and easiness in processing and using; after 3D printing is finished, densification of particles of the composite material is promoted by laser sintering and quenching, crystalline grains are refined, and therefore, the mechanical property of 3D printing products is improved.
Description
Technical field
The present invention relates to Graphene applied technical field, more particularly to a kind of 3D printing Graphene-nonmetallic-metal composite
Material, preparation method and application.
Background technology
Single-layer graphene film is made up of one layer of intensive carbon hexatomic ring, and without any fault of construction, 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 in organic chemistry phenyl ring knot ditch, it be it is current till best two
Dimension nano material.The Graphene prepared in reality does not only exist monolayer, there is multilamellar yet.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
Carrier mobility under 2630m2/g, room temperature is about 200,000 (cm2/ vs), it is known that one of intensity highest material, compares diamond
Also hard, strength ratio iron and steel best in the world is taller upper 100 times.Simultaneously it possesses good toughness again, and can bend,
The theoretical Young's moduluss of ideal graphite alkene reach 1.0TPa, and fracture strength is 130GPa.Heat conductivity is up to 5000W/mK, is current
Till highest.
At present, in the compound of grapheme material, modification application aspect has carried out more research to domestic and international research worker, 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 is by the material with porous material in searching nature, then passes through height with graphene oxide
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 is 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 ferrum 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 include by
Waste lithium iron phosphate battery positive plate is mixed by organic solvent immersion, ultrasonic Treatment, 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；Finally the LiFePO 4 material for obtaining and graphene oxide are mixed, 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 includes hydro-thermal operation, compound working procedure, and preparation method of the present invention causes stannic disulfide to exist
Graphenic surface directly carries out growth in situ, through washing, is dried and obtains lamellar 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 ferrum/graphene composite material are aoxidized, preparation method step includes
Hydro-thermal operation, compound working procedure, preparation method of the present invention causes iron sesquioxide nano-particle uniform load in three-dimensional grapheme
In surface and pore passage structure, through washing, be dried obtain sesquioxide/graphene composite material, the materials application in lithium from
Sub- battery, with high power capacity, have extended cycle life, low cost and easy excellent properties such as large-scale production.Chinese Patent Application No.：
CN201610764913.X, discloses a kind of preparation method of Manganese monosulfide ./graphene nanocomposite material, lithium ion battery and bears
Pole, lithium ion battery, preparation method step includes hydro-thermal operation, compound working procedure, and preparation method of the present invention causes Manganese monosulfide. in stone
Black alkene surface directly carries out growth in situ, through washing, is dried and obtains Manganese monosulfide ./graphene composite material, and the present invention passes through sulfur
The shortcomings of changing stability difference caused by manganese is combined to overcome its change in volume with three-dimensional redox graphene, strengthens 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 of microspheroidal structure and its synthetic method, belong to Micron-nano composites and prepare and synthesis
Technical field.Fill 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 nanometer 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 adopts 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, and the structure of matter of preparation is stablized, and changing parameter can change the pattern of material, enter
And the chemical property of lifting material, 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 is due to interfacial energy height, intermolecular active force and chemical bond work
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 3D printing Graphene-nonmetallic-metal composite
The preparation method of material.The 3D printing Graphene that the present invention is prepared-nonmetallic-metallic composite has high rigidity, height
Intensity, resistivity are low, are easily processed the superior function for using, and can be widely applied to the materials processings 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..
The present invention is achieved by the following technical solutions：
The preparation method of 3D printing Graphene-nonmetallic-metallic composite, it is characterised in that comprise the steps：
(1) by graphene quantum dot and/or graphene microchip, non-metal simple-substance and/or non-metallic under ultrasonication
Compound, metal simple-substance and/or metallic compound carry out mixed grinding shearing, and composite slurry material or composite powder material is obtained,
The ultrasonication is produced by ultrasonic head, ultrasonic device or Vltrasonic device, and the frequency of ultrasound is 10-100KHz, wherein Graphene amount
Son point and/or graphene microchip, non-metal simple-substance and/or nonmetallic compound, metal simple-substance and/or metallic compound three
Weight ratio is 1：(1~45)：(1~45)；
(2) obtained composite slurry material or powder body material are dried, obtain 3D printing Graphene-nonmetallic-gold
Category composite.
Further, the non-metal simple-substance is that sulfur, nitrogen, silicon, phosphorus, boron, fluorine, chlorine, arsenic, selenium, bromine, tellurium, iodine, astatine are nonmetallic
One or more in simple substance.
Further, the nonmetallic compound is boron nitride, CNT, carbon fiber, polyaniline, rare earth, rubber, modeling
One or more in material, polypyrrole, polythiophene, cationic resin, resin anion (R.A.).
Further, metal simple-substance be zirconium, titanium, lead, nickel, copper, silver, molybdenum, gold, palladium, zinc, aluminum, ferrum, cobalt, chromium, manganese, stannum,
One or more in iridium, ruthenium, indium, lanthanide series metal simple substance.
Further, metallic compound be zirconium oxide, molybdenum bisuphide, tungsten disulfide, lead oxide, vulcanized lead, nickel hydroxide,
Nickel oxide, nickel phosphide, copper oxide, silver oxide, Palladous chloride., Zinc Oxide, aluminium oxide, ferrum 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 hydrate., cadmium sulfide, oxygen
Change chromium, manganese oxide, stannum oxide, stibium oxide, tungsten oxide, bismuth oxide, yittrium oxide, zirconium oxide, Zirconium orthosilicate., yttrium oxide, iridium chloride, iridium
Complex, silver oxide, ruthenium-oxide, ruthenic acid are secret, one or more in ruthenic acid lead, Scia, Indium sesquioxide., magnesium oxide.
Used as a kind of embodiment, the mixed grinding shearing of step (1) is specifically carried out mixture under solid phase conditions
Physical grinding is sheared, it is preferable that grinding pressure is 1-200MPa, and milling time is 1-24h.Solid phase mixing under condition of high voltage is ground
Grind scissors and cut, not only cause mixture dispersion, mixing evenly, improve the uniformity of its dispersion mixing, more effectively reach prevention
The stacking and reunion of graphene quantum dot and/or graphene microchip, beneficial to the compound action and enhancing of Graphene and metallicses
Adhesion.
Used as another embodiment, the mixed grinding shearing of step (1) specifically enters mixture under liquid-phase condition
Row physical grinding is sheared, it is preferable that grinding pressure is 1-250MPa, and milling time is 1-12h, and temperature is 2-18 DEG C, the liquid
Phase condition be water, ethanol, acetone, Polyethylene Glycol, polyvinyl alcohol, Methanamide, N-Methyl pyrrolidone, acetonitrile, methanol, propanol,
Acetone, dioxane, tetrahydrofuran, butanone, n-butyl alcohol, ethyl acetate, ether, diisopropyl ether, dichloromethane, chloroform, bromine second
The combination of the solvent that one or more in alkane, benzene, carbon tetrachloride, Carbon bisulfide, hexamethylene, hexane, kerosene can dissolve each other.High pressure
Under the conditions of liquid phase physical grinding shearing, similarly can reach above-mentioned solid phase mixed grinding shearing effect, can also prevent under low temperature
Brownian movement violent when only there is high temperature is produced reunites again.Preferably, temperature is 4-6 DEG C.
Further, the drying meanss of step (2) are atmosphere pressure desiccation, low pressure seasoning, boulton process, supercritical drying
One kind in dry method or spray drying method, baking temperature is 30-1000 DEG C, and drying time is 10-600min.
The present invention also provides a kind of 3D printing Graphene-nonmetallic-metallic composite, it is characterised in that by above-mentioned
Preparation method is obtained.
The present invention also provides a kind of application of 3D printing Graphene-nonmetallic-metallic composite, it is characterised in that will
The 3D printing Graphene-nonmetallic-metallic composite is sintered, quenching Jing after 3D printing using laser system, laser
Frequency is 30-800kHz, and laser power is 30-300W, and spot diameter is 0.1-10mm, and scanning speed is 0.1-10mm/s, is swept
It is 0.1-2.0mm to retouch spacing, obtains laser sintered 3D printing product.
The invention has the beneficial effects as follows：
By the preparation method of 3D printing Graphene of the present invention-nonmetallic-metallic composite so that during Graphene application
Lamination and reunion are avoided, and the multiple metallicses composite of 3D printing Graphene prepared by the present invention, with high rigidity, high-strength
Degree, high heat conduction, resistivity are low, are easily processed the superior function for using, and Jing after 3D printing using laser sintered, quenching, promote
Composite material granular densification, and crystal grain thinning, so as to improve the mechanical performance of 3D printing product.Can be widely applied to tooth kind
The material processing fields such as plant, 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..
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 3D printing Graphene of the present embodiment-nonmetallic-metallic composite, its preparation method comprises the steps：
(1) under ultrasonic probe effect the frequency of ultrasound (be 10KHz) by graphene quantum dot and Zirconium oxide powder, rare earth
With 1：3：6 mass ratio is mixed, and mixture is sheared by the grinding of solvent high-pressure physics of Polyethylene Glycol, and pressure is 120MPa,
Time is 12h, and temperature is 2 DEG C, and composite slurry material is obtained；
(2) obtained composite slurry material is vacuum dried, pressure is 250Pa, drying time is 60min, is dried
Temperature is 50 DEG C, obtains 3D printing Graphene-nonmetallic-metallic composite.
In other embodiments, graphene quantum dot can also be with graphene microchip or graphene quantum dot and Graphene
The mixture of microplate is replacing；Vacuum drying pressure can be in the range of 150-1000Pa, and drying time is 60-120min,
Baking temperature is 30~50 DEG C.
Embodiment 2
The application process of the 3D printing Graphene of embodiment 1-nonmetallic-metallic composite is：By 3D printing Graphene-
Nonmetallic-metallic composite is sintered, quenching Jing after 3D printing using fiber laser system, and laser frequency is 80kHz,
Laser power is 190W, and spot diameter is 0.8mm, and scanning speed is 0.9mm/s, and sweep span is 0.9mm, obtains laser sintered 3D
Printed product.
Embodiment 3
The 3D printing Graphene of the present embodiment-nonmetallic-metallic composite, its preparation method comprises the steps：
(1) under ultrasound reactor effect the frequency of ultrasound (be 100KHz) by graphene microchip, titania powder,
Polyaniline is with 1:4:5 mass ratio is mixed, and is adopted ball mill pure water and is sheared for the grinding of solvent high-pressure physics, and pressure is
50MPa, the time is 1h, and temperature is 18 DEG C, and composite slurry material is obtained；
(2) obtained composite slurry material is carried out into constant pressure and dry, drying time is 60min, and baking temperature is 90 DEG C, is obtained
To 3D printing Graphene-nonmetallic-metallic composite.
In other embodiments, polyaniline can also be with boron nitride, CNT, carbon fiber, rare earth, rubber, plastics, poly-
Replacing, drying time of constant pressure and dry can be with for one or more in pyrroles, polythiophene, cationic resin, resin anion (R.A.)
In 100-500min, baking temperature is in the range of 50-120 DEG C.
Embodiment 4
The application process of the 3D printing Graphene of embodiment 3-nonmetallic-metallic composite is：By 3D printing Graphene-
Nonmetallic-metallic composite is sintered, quenching Jing after 3D printing using argon laser system, and laser frequency is
500kHz, laser power is 180W, and spot diameter is 0.7mm, and scanning speed is 0.3mm/s, and sweep span is 0.7mm, obtains sharp
Light sinters 3D printing product.
Embodiment 5
The 3D printing Graphene of the present embodiment-nonmetallic-metallic composite, its preparation method comprises the steps：
(1) under ultrasonic probe effect the frequency of ultrasound (be 50KHz) by graphene microchip, titania powder, rare earth
With 1:6:3 part by weight is mixed, and is sheared by the grinding of solvent high-pressure physics of pure water, and pressure is 250MPa, and the time is 2h,
Temperature is 4 DEG C, and composite powder material is obtained；
(2) obtained composite slurry material is spray-dried, drying time is 100min, baking temperature is 69 DEG C,
Obtain anhydrous composite powder material.
Embodiment 6
The application process of the 3D printing Graphene of embodiment 5-nonmetallic-metallic composite is：By 3D printing Graphene-
Nonmetallic-metallic composite is sintered, quenching Jing after 3D printing using carbon dioxide laser system, and laser frequency is
300kHz, laser power is 170W, and spot diameter is 0.5mm, and scanning speed is 0.3mm/s, and sweep span is 0.8mm, obtains sharp
Light sinters 3D printing product.
Embodiment 7
The 3D printing Graphene of the present embodiment-nonmetallic-metallic composite, its preparation method comprises the steps：
(1) under ultrasonic probe effect the frequency of ultrasound (be 10KHz) by graphene microchip and zirconium, sulfur with 1:1:1 weight
Amount ratio is mixed, and is sheared using solid phase physics polishing high pressure abrasive, and pressure is 1MPa, and the time is 1h, and composite pulp is obtained
Body material；
(2) obtained composite slurry material is spray-dried, drying time is 30min, drying time is 600min,
Obtain 3D printing Graphene-nonmetallic-metallic composite.
In other embodiments, zirconium can also by titanium, lead, nickel, copper, silver, molybdenum, gold, palladium, zinc, aluminum, ferrum, cobalt, chromium, manganese,
One or more replacements in stannum, iridium, ruthenium, indium, lanthanide series metal simple substance；Sulfur can also by nitrogen, silicon, phosphorus, boron, fluorine, chlorine, arsenic, selenium,
One or more replacements in bromine, tellurium, iodine, astatine.
Embodiment 8
The application process of the 3D printing Graphene of embodiment 7-nonmetallic-metallic composite is：By 3D printing Graphene-
Nonmetallic-metallic composite is sintered, quenching Jing after 3D printing using carbon dioxide laser system, and laser frequency is
30kHz, laser power is 30W, and spot diameter is 0.1mm, and scanning speed is 10mm/s, and sweep span is 0.1mm, obtains laser burning
Knot 3D printing product.
Embodiment 9
The 3D printing Graphene of the present embodiment-nonmetallic-metallic composite, its preparation method comprises the steps：
(1) under ultrasonic probe effect the frequency of ultrasound (be 100KHz) by graphene quantum dot and silicon, Zinc oxide powder
With 1:45:45 part by weight is mixed, and mixture is carried out under solid phase conditions high pressure abrasive shearing, and pressure is
200MPa, the time is 24h, and composite slurry material is obtained；
(2) obtained composite slurry material is carried out into supercritical drying, pressure is 500Pa, and temperature is 80 DEG C, drying time
For 10min, 3D printing Graphene-nonmetallic-metallic composite is obtained.
In other embodiments, silicon can also be by the one kind in sulfur, 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, copper oxide, silver oxide, Palladous chloride., Zinc Oxide, aluminium oxide, ferrum 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 hydrate., cadmium sulfide, oxygen
Change chromium, manganese oxide, stannum oxide, stibium oxide, tungsten oxide, bismuth oxide, yittrium oxide, zirconium oxide, Zirconium orthosilicate., yttrium oxide, iridium chloride, iridium
Complex, silver oxide, ruthenium-oxide, ruthenic acid are secret, one or more replacements in ruthenic acid lead, Scia, Indium sesquioxide., magnesium oxide.
Embodiment 10
The application process of the 3D printing Graphene of embodiment 9-nonmetallic-metallic composite is：By 3D printing Graphene-
Nonmetallic-metallic composite is sintered, quenching Jing after 3D printing using argon laser system, and laser frequency is
200kHz, laser power is 800W, and spot diameter is 10mm, and scanning speed is 0.1mm/s, and sweep span is 2mm, obtains laser burning
Knot 3D printing product.
Embodiment 11
The 3D printing Graphene of the present embodiment-nonmetallic-metallic composite, its preparation method comprises the steps：
(1) under ultrasonic probe effect the frequency of ultrasound (be 80KHz) by graphene quantum dot and graphene microchip, polyphenyl
Amine and silicon, Zirconium oxide powder and zirconium are mixed, wherein (graphene quantum dot and graphene microchip), (polyaniline and silicon), (oxygen
Change zirconium powder and zirconium) weight ratio be 1:20:20, mixture is carried out into high pressure abrasive shearing by solvent of acetone, pressure is
1MPa, the time is 6h, and temperature is 6 DEG C, and composite slurry material is obtained；
(2) obtained composite slurry material is vacuum dried, pressure is 1000Pa, drying time is 20min, is dried
Temperature is 1000 DEG C, obtains 3D printing Graphene-nonmetallic-metallic composite.
Above-mentioned embodiment is the invention is not limited in, if the various changes or deformation to the present invention are without departing from the present invention
Spirit and scope, if these change and deformation belong to the present invention claim and equivalent technologies within the scope of, then this
It is bright to be also intended to comprising these changes and deform.
Claims (10)
1.3D prints the preparation method of Graphene-nonmetallic-metallic composite, it is characterised in that comprise the steps：
(1) under ultrasonication by graphene quantum dot and/or graphene microchip, non-metal simple-substance and/or nonmetallic compound,
Metal simple-substance and/or metallic compound carry out mixed grinding shearing, and composite slurry material or composite powder material is obtained, described super
Sound effect by ultrasonic head, ultrasonic device or Vltrasonic device produce, ultrasound frequency be 10-100KHz, wherein graphene quantum dot and/
Or the weight ratio of graphene microchip, non-metal simple-substance and/or nonmetallic compound, metal simple-substance and/or metallic compound three
For 1：(1~45)：(1~45)；
(2) obtained composite slurry material or powder body material are dried, obtain 3D printing Graphene-nonmetallic-metal multiple
Condensation material.
2. the preparation method of 3D printing Graphene according to claim 1-nonmetallic-metallic composite, its feature exists
In：The non-metal simple-substance be sulfur, nitrogen, silicon, phosphorus, boron, fluorine, chlorine, arsenic, selenium, bromine, tellurium, iodine, astatine non-metal simple-substance in one kind or
It is several.
3. the preparation method of 3D printing Graphene according to claim 1-nonmetallic-metallic composite, its feature exists
In：The nonmetallic compound is boron nitride, CNT, carbon fiber, polyaniline, rare earth, rubber, plastics, polypyrrole, poly- thiophene
One or more in fen, cationic resin, resin anion (R.A.).
4. the preparation method of 3D printing Graphene according to claim 1-nonmetallic-metallic composite, its feature exists
In：Metal simple-substance is zirconium, titanium, lead, and nickel, copper, silver, molybdenum, gold, palladium, zinc, aluminum, ferrum, cobalt, chromium, manganese, stannum, iridium, ruthenium, indium, group of the lanthanides are golden
One or more in category simple substance.
5. the preparation method of 3D printing Graphene according to claim 1-nonmetallic-metallic composite, its feature exists
In：Metallic compound be zirconium oxide, molybdenum bisuphide, tungsten disulfide, lead oxide, vulcanized lead, nickel hydroxide, nickel oxide, nickel phosphide,
Copper oxide, silver oxide, Palladous chloride., Zinc Oxide, aluminium oxide, ferrum oxide, iron phosphide, cobalt sulfide, lead sulfate, LiFePO4, phosphoric acid
Manganese lithium, 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 manganese
Sour lithium, nickle cobalt lithium manganate, cobalt oxide, titanium oxide, titanium boride, vanadium oxide, Cadmium hydrate., cadmium sulfide, chromium oxide, manganese oxide, oxygen
Change stannum, stibium oxide, tungsten oxide, bismuth oxide, yittrium oxide, zirconium oxide, Zirconium orthosilicate., yttrium oxide, iridium chloride, iridium complex, silver oxide,
Ruthenium-oxide, ruthenic acid are secret, one or more in ruthenic acid lead, Scia, Indium sesquioxide., magnesium oxide.
6. the preparation method of 3D printing Graphene according to claim 1-nonmetallic-metallic composite, its feature exists
In：The mixed grinding of step (1) is sheared specifically by mixture carries out physical grinding shearing under solid phase conditions, and grinding pressure is
1-200MPa, milling time is 1-24h.
7. the preparation method of 3D printing Graphene according to claim 1-nonmetallic-metallic composite, its feature exists
In：The mixed grinding of step (1) is sheared specifically by mixture carries out physical grinding shearing under liquid-phase condition, and grinding pressure is
1-250MPa, milling time is 1-12h, and temperature is 2-18 DEG C, and the liquid-phase condition is water, ethanol, acetone, Polyethylene Glycol, poly-
Vinyl alcohol, Methanamide, N-Methyl pyrrolidone, acetonitrile, methanol, propanol, acetone, dioxane, tetrahydrofuran, butanone, just
Butanol, ethyl acetate, ether, diisopropyl ether, dichloromethane, chloroform, bromoethane, benzene, carbon tetrachloride, Carbon bisulfide, hexamethylene, oneself
The combination of the solvent that one or more in alkane, kerosene can dissolve each other.
8. the preparation method of 3D printing Graphene according to claim 1-nonmetallic-metallic composite, its feature exists
In：The drying meanss of step (2) are atmosphere pressure desiccation, low pressure seasoning, boulton process, supercritical drying or spray drying
One kind in method, baking temperature is 30-1000 DEG C, and drying time is 10-600min.
9.3D prints Graphene-nonmetallic-metallic composite, it is characterised in that by the arbitrary described system of claim 1~8
Preparation Method is obtained.
10.3D prints the application of Graphene-nonmetallic-metallic composite, it is characterised in that beat 3D described in claim 9
Print Graphene-nonmetallic-metallic composite is sintered, quenching Jing after 3D printing using laser system, and laser frequency is
30-800kHz, laser power is 30-300W, and spot diameter is 0.1-10mm, and scanning speed is 0.1-10mm/s, sweep span
For 0.1-2.0mm, laser sintered 3D printing product is obtained.
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