CN107236972B - A method of graphene/copper composite powder is prepared using electrodeposition process - Google Patents
A method of graphene/copper composite powder is prepared using electrodeposition process Download PDFInfo
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- CN107236972B CN107236972B CN201710247095.0A CN201710247095A CN107236972B CN 107236972 B CN107236972 B CN 107236972B CN 201710247095 A CN201710247095 A CN 201710247095A CN 107236972 B CN107236972 B CN 107236972B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
Abstract
A method of graphene/copper composite powder is prepared using electrodeposition process, it is characterized in that the following steps are included: using electrolytic copper foil as anode, copper foil is cathode, and the mixed solution of soluble copper salt, soluble nickel salt and graphene oxide is electrolyte, leads to direct current and carries out electro-deposition, keep certain current density for a period of time, products therefrom washes of absolute alcohol product will be deposited on cathode, remove residual impurity, place into vacuum oven and dried, grinding, obtains graphene/copper composite powder.It is big that the present invention solves the problems, such as that graphene uniform is dispersed in the difficulty in Copper substrate, so that graphene uniform is distributed on Copper substrate；The graphene prepared/copper composite powder pattern is rendered as uniform spherical shape, and graphene is dispersed in copper powder in the form of single layer or few layer；Simple process, operation are easy, and low in cost, sample preparation and electrodeposition process are without especial equipment requirements.
Description
Technical field
The invention belongs to metal powder preparation technical fields, are related to Metallic Functional Materials preparation.
Background technique
Graphene is because with high intensity and excellent electrical and thermal conductivity performance, (intensity is 130 GPa, carrier mobility
For 15000 cm2/ Vs, thermal coefficient are 5300 W/mK) and it is considered as the best strong of high-strength highly-conductive Cu-base composites
Change phase, but it is that graphene is strong that graphene uniform, which is dispersed in the big difficulty in Copper substrate and graphene and the interfacial combined function difference of copper,
Change two hang-ups in Cu-base composites preparation.
It is ball-milling method that graphene, which strengthens the most common method of Cu-base composites, but ball-milling method not can solve two above and ask
Topic.Kim W J, Lee T J, Han the S H. Multi-layer graphene/copper such as Kim composites:
Preparation using high-ratio differential speed rolling microstructure and
Mechanical properties, Carbon, 69, pp55-65,2014. is using the preparation of ball milling combination Differential speed rolling technology
Graphene and copper powder are mixed by high-energy ball milling method, are then rolled using Differential speed rolling technology by graphene Cu-base composites
System prepares multi-layer graphene enhancing Cu-base composites.Although ball milling combination rolling technique is conducive to graphene in Copper substrate
In dispersibility, the crystal grain of copper can also be refined and increase the uniformity of tissue, but the interface that can't resolve graphene and copper is tied
Close the problem of performance difference.Tang Y X, Yang X M, Wang R R, Li the M X. Enhancement of such as Tang the
mechanical properties of graphene-copper composites with graphene-nickel
Hybrids, Materials Science and Engineering A, 599, pp247-254,2014. using ball milling
Method mixes the graphene sheet layer and copper powder of Ni Nanoparticle Modified, can solve to a certain extent graphene uniform and be dispersed in
The problem of the interfacial combined function difference of difficulty in Copper substrate big problem and graphene and copper.Although the combination of Ni and graphene
The binding performance number of performance ratio Cu and graphene, but Ni and graphene cannot form primary bond (metallic bond, ionic bond after sintering
Or covalent bond) Xu Z P, Buehler M J. Interface structure and mechanics between
graphene and metal substrates: a first-principles study, Journal of Physics:
Condensed Matter, 22, pp485301,2010, so graphene and the copper powder mixing modified using Ni not
It can tackle the problem at its root.Li Bin graphene/Cu-base composites preparation and the Harbin performance study [D]: Harbin
Polytechnical university, the preparation of improvement molecular level mixed method, characterization and the performance of 2012. and Li Ruiyu graphene/copper composite material
The Wuhan [D]: Wuhan University of Technology is studied, 2014. utilize molecular level mixing method and its follow-on molecular level mixing method
(in H after graphene oxide and copper ion mixed solution are dried2Middle reduction), it has obtained graphene uniform and has been distributed in copper powder
In graphene/copper composite powder, but sintered alloy consistency is low, and alloy strength and conductivity are all less desirable.Thus
As it can be seen that although molecular level mixing method can solve graphene uniform and be dispersed in the big problem of difficulty in Copper substrate, it can not
Solve the problems, such as that the interfacial combined function of graphene and copper is poor.
It can be seen that although there are many graphene/copper composite powder preparation method, so far still without a kind of practical side
Method can solve that difficulty that graphene uniform is dispersed in Copper substrate is big and the interfacial combined function poor two of graphene and copper simultaneously
Hang-up develops new preparation method to solve graphene/copper composite powder of the more dominance of this two hang-up energy, has positive
Realistic meaning and good application prospect.
Summary of the invention
It is an object of the invention to be directed to existing technology of preparing and technologic deficiency, a kind of utilization electro-deposition legal system is provided
The method of standby graphene/copper composite powder.
The present invention is achieved by the following technical solutions.
A kind of use electro-deposition method of the present invention prepares graphene/copper composite powder, as follows.
Using electrolytic copper foil as anode, copper foil is cathode, and soluble copper salt, soluble nickel salt and graphene oxide are mixed
Solution is electrolyte, leads to direct current and carries out electro-deposition, certain current density is kept to deposit products therefrom on cathode for a period of time
As graphene/copper composite powder.
With washes of absolute alcohol product, residual impurity is removed, places into vacuum oven and is dried, ground, obtain
Graphene/copper composite powder.
The soluble copper salt is copper chloride, one of copper sulphate or copper nitrate.
The soluble nickel salt is nickel chloride, one of nickel sulfate or nickel nitrate.
The mass ratio of the mantoquita and nickel salt is 5:1-100:1.
The concentration of electrolyte is 0.01 g/ml-1.0 g/ml.
The current density is 5 A/m2-5000 A/m2。
The electrodeposition time is 2 h-48 h.
It is an advantage of the invention that.
(1) present invention has intended to solve that graphene uniform is dispersed in the big problem of the difficulty in Copper substrate, so that graphene is equal
It is even to be distributed on Copper substrate.
(2) a small amount of graphene is added, there is no the electric conductivity for reducing mixed solution, the graphene/copper prepared is compound
Powder pattern is rendered as uniform spherical shape, and graphene is dispersed in copper powder in the form of single layer or few layer.
(3) simple process, operation is easy, low in cost: raw material crystalline graphite powder, electrolytic copper foil, sodium nitrate, potassium permanganate
Etc. being common industrial raw material, sample preparation and electrodeposition process are without especial equipment requirements.
Detailed description of the invention
Fig. 1 is graphene/copper composite powder stereoscan photograph prepared by embodiment 1.
Specific embodiment
The present invention will be described further by following embodiment, and but the scope of the present invention is not limited thereto.
Embodiment 1.
Graphene/copper composite powder is prepared, should be sequentially included the following steps: using electrolytic copper foil as anode, copper foil is cathode, solvable
Property mantoquita copper sulphate (CuSO4) and soluble nickel salt nickel sulfate (NiSO4), by mantoquita: nickel salt=10:1 mass ratio, with oxidation stone
The black mixed solution of alkene is electrolyte, and concentration of electrolyte is 0.12 g/ml, leads to direct current and carries out electro-deposition, keeps 50 A/m2
24 h of current density, deposition products therefrom is graphene/copper composite powder on cathode.
Embodiment 2.
Graphene/copper composite powder is prepared, should be sequentially included the following steps: using electrolytic copper foil as anode, copper foil is cathode, solvable
Property mantoquita copper chloride (CuCl2) and soluble nickel salt nickel chloride (NiCl2), by mantoquita: nickel salt=20:1 mass ratio, with oxidation stone
The black mixed solution of alkene is electrolyte, and concentration of electrolyte is 0.15 g/ml, leads to direct current and carries out electro-deposition, keeps 100 A/
m248 h of current density, deposition products therefrom is graphene/copper composite powder on cathode.
Embodiment 3.
Graphene/copper composite powder is prepared, should be sequentially included the following steps: using electrolytic copper foil as anode, copper foil is cathode, solvable
Property mantoquita copper nitrate (CuNO3) and soluble nickel salt nickel nitrate (NiNO3), by mantoquita: nickel salt=15:1 mass ratio, with oxidation stone
The black mixed solution of alkene is electrolyte, and concentration of electrolyte is 0.60 g/ml, leads to direct current and carries out electro-deposition, keeps 80 A/m2
12 h of current density, deposition products therefrom is graphene/copper composite powder on cathode.
Claims (6)
1. a kind of prepare graphene/copper composite powder method using electrodeposition process, it is characterized in that the following steps are included: with cathode copper
Piece is anode, and copper foil is cathode, and the mixed solution of soluble copper salt, soluble nickel salt and graphene oxide is electrolyte, is led to straight
Galvanic electricity carries out electro-deposition, keeps certain current density for a period of time, and products therefrom washes of absolute alcohol will be deposited on cathode
Product removes residual impurity, places into vacuum oven and dried, and grinds, obtains graphene/copper composite powder.
2. according to claim 1 prepare graphene/copper composite powder method, it is characterized in that the soluble copper salt is
Copper chloride, one of copper sulphate or copper nitrate.
3. according to claim 1 prepare graphene/copper composite powder method, it is characterized in that the soluble nickel salt is
Nickel chloride, one of nickel sulfate or nickel nitrate.
4. according to claim 1 prepare graphene/copper composite powder method, it is characterized in that the mantoquita and nickel salt
Mass ratio is 5:1-100:1.
5. according to claim 1 prepare graphene/copper composite powder method, it is characterized in that the current density is 5
A/m2-5000 A/m2。
6. according to claim 1 prepare graphene/copper composite powder method, it is characterized in that the electrodeposition time is
2 h-48 h。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110158123A (en) * | 2019-05-10 | 2019-08-23 | 东北大学 | A kind of surface metalation graphene and preparation method thereof |
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| CN112599717B (en) * | 2020-12-17 | 2021-11-26 | 上海交通大学 | Lithium ion battery optimization method based on surface electro-deposition metal/graphene composite layer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174702A (en) * | 2011-01-11 | 2011-09-07 | 湖南大学 | Preparation method for metallic nano-particle and graphene composite |
| CN102896834A (en) * | 2012-10-11 | 2013-01-30 | 湖南大学 | Graphene-copper nanoparticle composite, and preparation and application thereof |
| CN105603231A (en) * | 2015-12-07 | 2016-05-25 | 宁波墨西科技有限公司 | Graphene-modified copper alloy nano-material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174702A (en) * | 2011-01-11 | 2011-09-07 | 湖南大学 | Preparation method for metallic nano-particle and graphene composite |
| CN102896834A (en) * | 2012-10-11 | 2013-01-30 | 湖南大学 | Graphene-copper nanoparticle composite, and preparation and application thereof |
| CN105603231A (en) * | 2015-12-07 | 2016-05-25 | 宁波墨西科技有限公司 | Graphene-modified copper alloy nano-material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110158123A (en) * | 2019-05-10 | 2019-08-23 | 东北大学 | A kind of surface metalation graphene and preparation method thereof |
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