CN106623976A - Preparation method of graphene-metal-based bulk composite material - Google Patents
Preparation method of graphene-metal-based bulk composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 72
- 239000000843 powder Substances 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims description 37
- 239000010949 copper Substances 0.000 claims description 37
- 239000004332 silver Substances 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 28
- 239000008187 granular material Substances 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 238000005054 agglomeration Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims 1
- 229910001960 metal nitrate Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- 239000002905 metal composite material Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- 238000005485 electric heating Methods 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- 238000002525 ultrasonication Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B22F1/0003—
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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Abstract
The invention discloses a preparation method of a graphene-metal-based bulk composite material. The preparation method of the graphene-metal-based bulk composite material comprises the steps of dispersing graphene oxide in deionized water for ultrasonic dispersing; dispersing metal salt in absolute ethyl alcohol for ultrasonic dispersing; mixing the two components, adding hydrazine hydrate for reduction reaction, sequentially washing a product with deionized water and absolute ethyl alcohol after completing reaction, removing a solvent, and finally drying to obtain graphene-loaded metal composite powder; dispersing the graphene-loaded metal composite powder into absolute ethyl alcohol, smashing and dispersing, then adding nano-metal powder, continuously ultrasonic dispersing, and plasma sintering at a vacuum state after drying to obtain the graphene-metal-based bulk composite material. According to the graphene-metal-based bulk composite material obtained through the invention, graphene is not agglomerated or oxidized, the electrical conductivity of the graphene-metal-based bulk composite material obtained through the invention is better than the electrical conductivity of the graphene-metal-based bulk composite material provided in the current research.
Description
Technical field
The invention belongs to graphene composite material technical field, and in particular to a kind of Graphene-Metal Substrate block composite wood
The preparation method of material.
Background technology
Graphene is a kind of similar cellular two-dimensional crystal lattice flat thin being arranged in sp2 hybridized orbits by carbon atom
Film, thickness is about 0.335nm, is material most thin in the world, and the specific surface area with super large is to be currently known intensity highest
Material, achieves many surprising progress in many fields in recent years, and is expected to most realize application soon in field of compound material.But
The graphene composite material for being seen in report is concentrated mainly on Graphene/polymer composites field, but so far with regard to stone
The rare report of mechanical property research of black alkene/metallic composite.
Many metals have high heat conduction, conductive and forming property, are the important matrix materials for preparing above-mentioned composite, profit
With the advantages of the high intensity of Graphene, high-conductivity and the mouldability of metal is expected to develop the graphite with Good All-around Property
Alkene/metallic composite, this respect research work theoretically or using upper all has attractive prospect.But due to graphite
The effect of the Van der Waals force existed between alkene lamella so that the reunion of Graphene is irreversible, in current relevant Graphene metal
Composite is prepared in pertinent literature report, and majority limitation is directly added into a metal Graphene, more using high energy spheroidal graphite method,
Matter machine etc. carries out mixed powder, mixes Graphene and easily occurs agglomeration in powder, and the performance of material greatly reduces.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Graphene-Metal Substrate block composite material, solves existing
There is the problem reunited in metal nano powder mixed process in preparation method Graphene.
The technical solution adopted in the present invention is, a kind of preparation method of Graphene-Metal Substrate block composite material, including
Following steps：
Step 1, by graphene oxide ultrasonic disperse in deionized water is disperseed；Slaine is scattered in absolute ethyl alcohol and is surpassed
Sound disperses.
Step 2, graphene oxide solution and metal salt solution are mixed, while add hydrazine hydrate to carry out reduction reaction, instead
By product successively deionized water and absolute ethanol washing after should finishing, solvent is removed, be finally dried, obtain the graphite of non-oxidation
The composite granule of alkene carried metal.
Step 3, the composite granule that step 2 is obtained is scattered in absolute ethyl alcohol, broken, decentralized processing, is then added
Nano metal powder, continues ultrasonic disperse, and after being dried Graphene-metal-based compound powder is obtained.
Step 4, powder is obtained under vacuum conditions by step 3, carries out plasma agglomeration, that is, obtain Graphene-Metal Substrate
Block composite material.
Of the invention the characteristics of, also resides in：
Metal of the present invention is copper or silver, i.e. Graphene-copper-based block composite material or Graphene-silver-based block composite wood
Material.
When metal be copper when, in step 1 graphene oxide be 1～2 mass parts, deionized water be 1～2 mass parts, sulfuric acid
Copper is 3～5 mass parts, and copper sulphate is 15～25 with the mass volume ratio of absolute ethyl alcohol：1mg/ml；When metal is silver, oxidation
Graphene is 1～2 mass parts, and deionized water is 10～20 mass parts, and silver nitrate is 5～16 mass parts, silver nitrate and anhydrous second
The mass volume ratio of alcohol is 2.5～8：1mg/ml.
The reduction reaction time is 1-3 hours in step 2, and reaction temperature is 60-90 DEG C.
The mass volume ratio of composite granule and absolute ethyl alcohol is 1 in step 3：0.6～1.2mg/ml.
Nano metal powder particle diameter is 200～500nm in step 3, and its quality is 1 with the mass volume ratio of absolute ethyl alcohol：5
～10g/ml.
Crush in step 3, decentralized processing is：The ultrasound 10-30 in ultrasonic power is for the cell disruptor of 1800-2500W
Minute；Add the Nano metal powder last continuation ultrasonic disperse 10-30 minutes under equal-wattage.
Plasma agglomeration is specially in step 4：Under vacuum conditions, 600 are heated to the programming rate of 100 DEG C/min～
900 DEG C, under 30～40MPa pressure, it is incubated 5～10min.The present invention with graphene oxide, slaine as raw material, by add
Reducing agent carries out reduction reaction and graphene-supported silver, the composite of copper ion is obtained, and mainly reaches Graphene using ultrasound
Purpose that is dispersed and reducing Graphene thickness.Ultrasonic Pulverization is when ultrasonic vibration is delivered in liquid, due to the sound intensity very
Greatly, very strong cavitation effect can be in a liquid excited, so as to produce substantial amounts of cavitation bubble in a liquid.With these cavitation gas
Bubble is produced and explosion, will produce microjet, and then the solid particle in liquid is smashed.Simultaneously because the vibration of ultrasonic wave, makes
Solid-liquid more fully dispersion mixing is uniform.Silver, copper nano is set to enter it again while ultrasonic explosion separates graphene layer
In, it is possible to Graphene interfloor distance is pulled open, the scattered purpose of graphene uniform is reached.
The invention has the beneficial effects as follows, compared with the mixed powder of existing high-energy ball milling, Graphene-Metal Substrate that the present invention is obtained is multiple
Graphene in condensation material powder does not produce reunion and without being oxidized, and mixes that the powder used time is short, efficiency high, while using simplest
Drying means, reduces cost, it is therefore prevented that oxidation.Process stabilizing, solves the problems, such as that well Graphene is easily reunited.Powder is burnt
After knot, electric conductivity of the electric conductivity better than the Graphene-Metal Substrate block composite material mentioned in research at present, the preparation have been obtained
Technological operation is simple, equipment investment is low, reliable in quality, is adapted to industrialization large-scale production.
Description of the drawings
Fig. 1 is that scale is 2 μm of stereoscan photographs under Graphene of the present invention-copper-based composite granule microcosmic；
Fig. 2 is Graphene of the present invention-copper-based composite granule energy spectrum diagram；
Fig. 3 is Graphene of the present invention-copper-based composite granule X-ray diffractogram；
Fig. 4 is the optical photograph of Graphene of the present invention-copper-based block composite material；
Fig. 5 is that scale is 1 μm of scanning electron microscope (SEM) photograph under Graphene of the present invention-silver-based composite granule microcosmic；
Fig. 6 is Graphene of the present invention-silver-based composite granule energy spectrum diagram；
Fig. 7 is the transmission electron microscope picture that scale is 100nm under Graphene of the present invention-silver-based composite granule microcosmic；
Fig. 8 is the X-ray diffractogram of Graphene of the present invention-silver-based composite granule；
Fig. 9 is the optical photograph of Graphene of the present invention-silver-based block composite material.
Specific embodiment
With reference to the accompanying drawings and detailed description the present invention is described in further detail, but the present invention is not limited to
These embodiments.
Present invention metallic on graphene sheet layer intermediate adsorbent first with oxidation-reduction method, increases graphene film
After the distance of layer, the method for then employing ultrasonic disperse is added to the Graphene for being loaded with copper particle in copper powder, Ran Houjin
Row plasma sintering is obtained block composite material.The present invention is specifically introduced by following examples to the method.
Embodiment 1
Step 1, by the mass parts of graphene oxide 2 in 1 mass parts deionized water, disperses under 40KHz ultrasonic environments
The mass parts of copper sulphate 3 and 10ml absolute ethyl alcohols are disperseed 2h by 2h under 40KHz ultrasonic environments.
Step 2, above-mentioned copper-bath is mixed with graphene oxide solution, and proceeds to enter in 80 DEG C of thermostat water bath
Row electromagnetic agitation, at the same add 6ml hydrazine hydrates (mass ratio is 75%), react 2 hours, be cooled to room temperature, by solid product according to
Secondary deionized water and each centrifugal treating of absolute ethyl alcohol three times, and be dried at less than 60 DEG C using electric heating cover, obtain anaerobic
The composite granule of the graphene-supported copper changed.
Step 3, takes the graphene-supported copper composite powders 0.5g for preparing, and the absolute ethyl alcohol of 300ml burns in 500ml
Mixed in cup, crushed in ultrasonic power is for the cell disruptor of 2200W, decentralized processing 20 minutes, added 30g
Copper powder (particle diameter 500nm), carries out again ultrasonication, dispersion, mixes 20 minutes under same ultrasound condition, the powder after dispersion is existed
It is dried using electric heating cover at 60 DEG C, you can obtain that layer is thin and finely dispersed Graphene-copper-based powder.
Step 4, by Graphene-copper-based powder under vacuum state (0.1Pa), is heated with the programming rate of 100 DEG C/min
To 900 DEG C, under 30MPa pressure, 10min is incubated, obtains Graphene-copper-based block composite material.
Embodiment 2
Step 1, by the mass parts of graphene oxide 2 in 2 mass parts deionized waters, disperses under 40KHz ultrasonic environments
The mass parts of copper sulphate 5 and 10ml absolute ethyl alcohols are disperseed 2h by 2h under 40KHz ultrasonic environments.
Step 2, above-mentioned copper-bath is mixed with graphene oxide solution, and proceeds to enter in 80 DEG C of thermostat water bath
Row electromagnetic agitation, at the same add 6ml hydrazine hydrates (mass ratio is 75%), react 1 hour, be cooled to room temperature, by solid product according to
Secondary deionized water and each centrifugal treating of absolute ethyl alcohol three times, and be dried at 60 DEG C using electric heating cover, obtain non-oxidation
The composite granule of graphene-supported copper.
Step 3, the absolute ethyl alcohol for taking the graphene-supported copper composite powders 0.3g and 300ml that step 2 is prepared exists
Mixed in 500ml beakers, crushed in ultrasonic power is for the cell disruptor of 1800W, decentralized processing 30 minutes, then
30g copper powders (particle diameter 200nm) are added, ultrasonication, dispersion is carried out under same ultrasound condition again, is mixed 30 minutes, after dispersion
Powder be dried using electric heating cover at 60 DEG C, you can obtain that layer is thin and finely dispersed Graphene-copper-based powder.
Step 4, by Graphene-copper-based powder under vacuum state (0.1Pa), is heated with the programming rate of 100 DEG C/min
To 900 DEG C, under 30MPa pressure, 10min is incubated, obtains Graphene-copper-based block composite material.
Embodiment 3
Step 1, by the mass parts of graphene oxide 1 in 2 mass parts deionized waters, disperses under 40KHz ultrasonic environments
The mass parts of copper sulphate 4 and 10ml absolute ethyl alcohols are disperseed 2h by 2h under 40KHz ultrasonic environments.
Step 2, above-mentioned copper-bath is mixed with graphene oxide solution, and proceeds to enter in 60 DEG C of thermostat water bath
Row electromagnetic agitation, at the same add 8ml hydrazine hydrates (mass ratio is 75%), react 3 hours, be cooled to room temperature, by solid product according to
Secondary deionized water and each centrifugal treating of absolute ethyl alcohol three times, and be dried at less than 60 DEG C using electric heating cover, obtain anaerobic
The composite granule of the graphene-supported copper changed.
Step 3, takes the graphene-supported copper composite powders 0.6g that step 2 is prepared, and the absolute ethyl alcohol of 300ml exists
Mixed in 500ml beakers, crushed in ultrasonic power is for the cell disruptor of 2500W, decentralized processing 10 minutes, then
30g copper powders (particle diameter 300nm) are added, ultrasonication, dispersion is carried out under same ultrasound condition again, is mixed 10 minutes, after dispersion
Powder be dried using electric heating cover at 60 DEG C, you can obtain that layer is thin and finely dispersed Graphene-copper-based powder.
Step 4, by Graphene-copper-based powder under vacuum state (0.1Pa), is heated with the programming rate of 100 DEG C/min
To 900 DEG C, under 30MPa pressure, 10min is incubated, obtains Graphene-copper-based block composite material.
Embodiment 4
Step 1, by the mass parts of graphene oxide 1 in 10 mass parts deionized waters, disperses under 40KHz ultrasonic environments
The mass parts of silver nitrate 5 and 10ml absolute ethyl alcohols are disperseed 2h by 2h under 40KHz ultrasonic environments；
Step 2, silver nitrate solution is poured into graphene dispersing solution in the thermostat water bath for proceeding to 80 DEG C carries out electromagnetism and stirs
Mix, while adding 5ml, the hydration hydrazine reaction 2h that concentration is 75%, be cooled to room temperature, distinguished using deionized water and absolute ethyl alcohol
Centrifugal treating 3 times, is dried using electric heating cover at less than 60 DEG C, obtains the composite granule of the graphene-supported silver of non-oxidation；
Step 3, the graphene-supported argentum composite powder body 0.5g that step 2 is obtained and absolute ethyl alcohol 300ml mix, in ultrasound
Power in the cell disruptor of 2200W to be crushed, decentralized processing 20min, adds the silver that 30g, average grain diameter are 400nm
Powder carries out ultrasonication, dispersion, mixing 20min, is dried using electric heating cover at 60 DEG C, that is, obtain being directly used in preparation
The Graphene of block-silver-based composite granule,
Step 4, the powder that step 3 is obtained is poured into the graphite jig of a diameter of 22cm, under vacuum state (0.1Pa),
600 DEG C are heated to the programming rate of 100 DEG C/min, under 40MPa pressure, 5min is incubated, Graphene-silver-based block are obtained and is answered
Condensation material.
Embodiment 5
Step 1, by the mass parts of graphene oxide 2 in 13 mass parts deionized waters, disperses under 40KHz ultrasonic environments
The mass parts of silver nitrate 10 and 10ml absolute ethyl alcohols are disperseed 2h by 2h under 40KHz ultrasonic environments；
Step 2, silver nitrate solution is poured into graphene dispersing solution in the thermostat water bath for proceeding to 70 DEG C carries out electromagnetism and stirs
Mix, while adding 5ml, the hydration hydrazine reaction 1.5h that concentration is 75%, be cooled to room temperature, using deionized water and absolute ethyl alcohol point
Other centrifugal treating 3 times, is dried using electric heating cover at less than 60 DEG C, obtains the composite powder of the graphene-supported silver of non-oxidation
Body；
Step 3, the graphene-supported argentum composite powder body 0.5g that step 2 is obtained and absolute ethyl alcohol 300ml mix, in ultrasound
Power in the cell disruptor of 2200W to be crushed, decentralized processing 10min, adds the silver that 30g, average grain diameter are 400nm
Powder carries out ultrasonication, dispersion, mixing 15min, is dried using electric heating cover at 60 DEG C, that is, obtain being directly used in preparation
The Graphene of block-silver-based composite granule,
Step 4, the powder that step 3 is obtained is poured into the graphite jig of a diameter of 22cm, under vacuum state (0.1Pa),
600 DEG C are heated to the programming rate of 100 DEG C/min, under 40MPa pressure, 5min is incubated, Graphene-silver-based block are obtained and is answered
Condensation material.
Embodiment 6
Step 1, by the mass parts of graphene oxide 1.5 in 20 mass parts deionized waters, divides under 40KHz ultrasonic environments
The mass parts of silver nitrate 16 and 10ml absolute ethyl alcohols are disperseed 2h by scattered 2h under 40KHz ultrasonic environments；
Step 2, silver nitrate solution is poured into graphene dispersing solution in the thermostat water bath for proceeding to 90 DEG C carries out electromagnetism and stirs
Mix, while adding 5ml, the hydration hydrazine reaction 1h that concentration is 75%, be cooled to room temperature, distinguished using deionized water and absolute ethyl alcohol
Centrifugal treating 3 times, is dried using electric heating cover at less than 60 DEG C, obtains the composite granule of the graphene-supported silver of non-oxidation；
Step 3, the graphene-supported argentum composite powder body 0.5g that step 2 is obtained and absolute ethyl alcohol 300ml mix, in ultrasound
Power in the cell disruptor of 2200W to be crushed, decentralized processing 15min, adds the silver that 30g, average grain diameter are 400nm
Powder carries out ultrasonication, dispersion, mixing 10min, is dried using electric heating cover at 60 DEG C, that is, obtain being directly used in preparation
The Graphene of block-silver-based composite granule,
Step 4, the powder that step 3 is obtained is poured into the graphite jig of a diameter of 22cm, under vacuum state (0.1Pa),
600 DEG C are heated to the programming rate of 100 DEG C/min, under 40MPa pressure, 5min is incubated, Graphene-silver-based block are obtained and is answered
Condensation material.
By taking embodiment 1 as an example, the structure and performance of Graphene of the present invention-copper-based block composite material are detected, will
The block that the method is obtained is roughly ground, fine grinding, polishing, metallographic observation, electrical conductivity test are carried out after corrosion.Its pattern such as Fig. 1
Shown, from Fig. 1 it can clearly be seen that thin graphene is wrapped up, is wrapped between copper particle, Fig. 2 shows that Graphene is copper-based multiple
Close the content situation of powder selected areas, hence it is evident that it can be seen that composition is essentially carbon, copper and minimal amount of oxygen, the content of oxygen is almost
Can ignore, illustrate that the powder prepared almost is not oxidized.From the XRD of Fig. 3, in the composite granule three are found that
The diffraction maximum (111) of individual copper, (200), (220), do not find other diffraction maximums, explanation in addition to these three diffraction maximums
Copper in mixed powder is not aoxidized；Because Graphene addition is less in mixed powder, fail the diffraction maximum for finding carbon.By
The optical photograph of Fig. 4 block materials can see, graphene uniform is dispersed on Copper substrate.From electrical conductivity test result table 1
From the point of view of, electrical conductivity is substantially better than the result of study in current document.
The Graphene of table 1-copper-based block composite material electric conductivity test result (fine copper electrical conductivity is 58)
By taking embodiment 4 as an example, the structure and performance of Graphene of the present invention-silver-based block composite material are detected, will
The block that the method is obtained is roughly ground, fine grinding, polishing, metallographic observation, electrical conductivity test are carried out after corrosion.Can be with by Fig. 5-8
Find out, graphene layer is thin in composite granule and uniform ring around dispersion and be wrapped in around silver particles；From the composite granule for preparing
From the point of view of power spectrum and XRD spectrum, composite granule non-oxidation illustrates not producing oxidation in heating and drying mode in course of reaction.From
Optical photograph Fig. 9 of silver-based block composite material can see that being dispersed on silver matrix for graphene uniform is tested from electrical conductivity
As a result from the point of view of table 2, electric conductivity is up to 85.98%IACS.
2 Graphenes of table-silver-based block composite material electric conductivity test result (fine silver electrical conductivity is 62.5)
Claims (8)
1. the preparation method of a kind of Graphene-Metal Substrate block composite material, it is characterised in that comprise the following steps：
Step 1, by graphene oxide ultrasonic disperse in deionized water is disperseed；Slaine is scattered in into ultrasound point in absolute ethyl alcohol
Dissipate；
Step 2, graphene oxide solution and metal salt solution are mixed, while adding hydrazine hydrate to carry out reduction reaction, have been reacted
By product successively deionized water and absolute ethanol washing after finishing, solvent is removed, be finally dried, the Graphene for obtaining non-oxidation is born
Carry the composite granule of metal；
Step 3, the composite granule that step 2 is obtained is scattered in absolute ethyl alcohol, broken, decentralized processing, then adds nanometer
Metal dust, continues ultrasonic disperse, and after being dried Graphene-metal-based compound powder is obtained；
Step 4, powder is obtained under vacuum conditions by step 3, carries out plasma agglomeration, that is, obtain Graphene-Metal Substrate block
Composite.
2. the preparation method of Graphene according to claim 1-Metal Substrate block composite material, it is characterised in that described
Metal is copper or silver, and metal nitrate is copper sulphate or silver nitrate.
3. the preparation method of Graphene according to claim 2-Metal Substrate block composite material, it is characterised in that work as institute
State metal for copper when, in step 1 graphene oxide be 1～2 mass parts, deionized water be 1～2 mass parts, copper sulphate be 3～5
Mass parts, copper sulphate is 15～25 with the mass volume ratio of absolute ethyl alcohol：1mg/ml；When the metal is silver, graphite oxide
Alkene is 1～2 mass parts, and deionized water is 10～20 mass parts, and silver nitrate is 5～16 mass parts, silver nitrate and absolute ethyl alcohol
Mass volume ratio is 2.5～8：1mg/ml.
4. the preparation method of Graphene according to claim 2-Metal Substrate block composite material, it is characterised in that step 2
Described in the reduction reaction time be 1-3 hours, reaction temperature be 60-90 DEG C.
5. the preparation method of Graphene according to claim 2-Metal Substrate block composite material, it is characterised in that step 3
Described in composite granule and absolute ethyl alcohol mass volume ratio be 1：0.6～1.2mg/ml.
6. the preparation method of Graphene according to claim 2-Metal Substrate block composite material, it is characterised in that step 3
Described in nano metal powder particle diameter be 200～500nm, the mass volume ratio of its quality and absolute ethyl alcohol is 1：5～10g/ml.
7. the preparation method of Graphene according to claim 2-Metal Substrate block composite material, it is characterised in that step 3
Described in crush, decentralized processing be：The ultrasound 10-30 minutes in ultrasonic power is for the cell disruptor of 1800-2500W；Adding
Enter the Nano metal powder last continuation ultrasonic disperse 10-30 minutes under equal-wattage.
8. the preparation method of Graphene according to claim 2-Metal Substrate block composite material, it is characterised in that step 4
Described in plasma agglomeration be specially：Under vacuum conditions, 600～900 DEG C are heated to the programming rate of 100 DEG C/min,
Under 30～40MPa pressure, 5～10min is incubated.
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