CN113270232B - Preparation method of graphene-copper composite ultrahigh-conductivity material - Google Patents
Preparation method of graphene-copper composite ultrahigh-conductivity material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 44
- 239000010949 copper Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 239000004020 conductor Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000001291 vacuum drying Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 238000005070 sampling Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical group O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical group CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- BXTSXFDFZMHCFO-UHFFFAOYSA-N OC1(C(C=NO)C=C(C=C1)CCCCCCCCC)O Chemical compound OC1(C(C=NO)C=C(C=C1)CCCCCCCCC)O BXTSXFDFZMHCFO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- YRWWOAFMPXPHEJ-OFBPEYICSA-K sodium L-ascorbic acid 2-phosphate Chemical compound [Na+].[Na+].[Na+].OC[C@H](O)[C@H]1OC(=O)C(OP([O-])([O-])=O)=C1[O-] YRWWOAFMPXPHEJ-OFBPEYICSA-K 0.000 claims description 4
- 229940048058 sodium ascorbyl phosphate Drugs 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims 1
- 235000010323 ascorbic acid Nutrition 0.000 claims 1
- 239000011668 ascorbic acid Substances 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 229930003268 Vitamin C Natural products 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000019154 vitamin C Nutrition 0.000 description 6
- 239000011718 vitamin C Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- 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
- B22F9/02—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
-
- 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
-
- 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
- B22F9/02—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
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Thermal Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a graphene-copper composite ultrahigh-conductivity material, and belongs to the technical field of new materials. The method comprises the following steps: s11, mixing the ionized water with copper salt, a reducing agent and a surfactant, mixing with an extracting agent, mixing with graphene, reacting at high temperature, centrifuging to obtain a solid substance, cleaning, and drying in vacuum; s12, oxidizing; s13, mixing the copper powder and ball milling; s14, vacuum drying; s15, roasting to obtain the graphene-copper composite powder, namely the graphene-copper composite ultrahigh conductive material. According to the preparation method of the graphene-copper composite ultrahigh conductive material, the copper powder obtained by copper salt reduction and the graphene are primarily dispersed, so that the ball milling uniformity of the graphene and the copper powder is improved, the agglomeration phenomenon under the high graphene content can be reduced, and the obtained ultrahigh conductive material has good strength and conductivity.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a preparation method of a graphene-copper composite ultrahigh-conductivity material.
Background
The copper wire has good electric conductivity, heat conductivity, corrosion resistance and processability. Graphene is widely introduced in the preparation of metal composite materials due to its mechanical properties, thermal conductivity and thermal expansion properties.
In the preparation of the graphite-copper composite material, the higher the graphene content is, the better the conductivity is. However, the higher the graphene content, the worse the dispersion of graphene and copper powder, which significantly reduces the strength and conductivity of the resulting composite material. The chemical reduction method is applied to the preparation of copper powder due to the characteristics of uniform powder, controllable particle size distribution, no agglomeration and the like.
Disclosure of Invention
According to the invention, copper reduction reaction is carried out in a liquid phase system, so that copper particles are extracted by the extraction liquid containing graphene, and a uniformly dispersed mixture can be obtained, thereby improving the uniformity of ball-milling and mixing of graphene and copper powder.
The invention discloses a preparation method of a graphene-copper composite ultrahigh-conductivity material, which comprises the following steps:
s11, mixing the ionized water with copper salt, a reducing agent and a surfactant, mixing with an extracting agent, mixing with graphene, reacting at high temperature, centrifuging to obtain a solid substance, cleaning, and drying in vacuum;
s12, oxidizing;
s13, mixing the copper powder and ball milling;
s14, vacuum drying;
and S15, roasting in a hydrogen atmosphere to obtain the graphene-copper composite powder, namely the graphene-copper composite ultrahigh conductive material.
In some embodiments of the invention, in S11, the copper salt is copper chloride dihydrate.
In some embodiments of the invention, in S11, the reducing agent is vitamin C or sodium ascorbyl phosphate, preferably sodium ascorbyl phosphate.
In some embodiments of the invention, in S11, the surfactant is polyethylene glycol 4000.
In some embodiments of the invention, in S11, the extractant is trioctylamine or 2-hydroxy-5-nonylsalicylaldoxime, preferably 2-hydroxy-5-nonylsalicylaldoxime.
In some embodiments of the present invention, in S11, the weight ratio of the copper salt, the reducing agent, the surfactant, the extractant, and the graphene is 0.1: (0.4-0.6): (0.005-0.02): (0.3-0.5): (0.1-0.3).
In some embodiments of the present invention, the high temperature reaction is 110-125 ℃ for 15-20h in S11.
In some embodiments of the present invention, in S11, the vacuum drying is at 50-60 ℃ for 3-4 h.
In some embodiments of the present invention, in S12, the oxidation treatment is 600-650 ℃ for 3-4 h.
In some embodiments of the invention, in S13, the weight ratio of the grinding balls to the materials is (15-20): 1, the rotation speed of the ball mill is 20-30rpm, and the ball milling is carried out for 10-15 h.
In some embodiments of the invention, in S14, the vacuum drying is at 50-60 ℃ for 3-4 h.
In some embodiments of the present invention, the calcination temperature in S15 is 200-250 deg.C, and the calcination time is 2.5-3 h.
In some embodiments of the present invention, in S11, after the concentration Cs of the surfactant is determined, the concentration of the extractant Ce is determined by the following formula:
wherein, CSAnd Ce in g/100mL, a in the range of 30-50, b in the range of 20-30.
In some embodiments of the invention, in S11, the high temperature reaction is performed in a pressure vessel, and the temperature rise control of the pressure vessel is performed by the following PID algorithm:
wherein, the delta u (c) corresponds to the variation of the temperature in the time interval of two testing temperatures; kc is constant, 12-15; f (C) is the deviation at the time of sampling C, f (C-1) is the deviation at the time of sampling C-1, and f (C-2) is the deviation at the time of sampling C-2; t isS1-2s, T, for a sampling periodIIntegration time is 1-1.5 min; t isDThe differential time is 1-1.5 min.
The beneficial technical effects of the invention are as follows:
(1) according to the preparation method of the graphene-copper composite ultrahigh conductive material, the copper powder obtained by copper salt reduction and the graphene are primarily dispersed, so that the ball milling uniformity of the graphene and the copper powder is improved, the agglomeration phenomenon under the high graphene content can be reduced, and the obtained ultrahigh conductive material has good strength and conductivity.
(2) In the preparation method of the graphene-copper composite ultrahigh conductive material, the extraction agent is mixed with the reduced copper obtained by extraction at any time, so that the graphene is uniformly dispersed in the mixture;
(3) according to the preparation method of the graphene-copper composite ultrahigh-conductivity material, the mixture of the reduced copper and the graphene is subjected to high-temperature treatment in the tube furnace, so that the ball milling efficiency of the graphene and the copper powder can be improved, possibly because the high-temperature treatment degrades the residual reducing agent, the surfactant and the extractant; it is also possible that the reduced copper particles are oxidized again to affect the hydrogen reduction process in the firing.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The experimental procedures used in the following examples and comparative examples are conventional ones unless otherwise specified. The graphene is a graphene nanosheet, the thickness of the graphene is 6-8nm, and the width of the graphene is 15 micrometers; the copper powder is 400-mesh atomized copper powder.
In the following examples and comparative examples, unless otherwise specified, parallel tests were conducted with the same components, contents, operating procedures and parameters.
Example 1
A preparation method of a graphene-copper composite ultrahigh conductive material comprises the following steps:
(1) adding 0.1g of copper chloride dihydrate and 0.5g of vitamin C into 25ml of deionized water, adding 40000.01 g of polyethylene glycol, and uniformly stirring. Adding 0.4g of trioctylamine, performing ultrasonic treatment for 15min to obtain milky liquid, adding 0.2g of graphene, performing ultrasonic treatment for 15min, and keeping the temperature in an anticorrosive pressure container at 125 ℃ for 16 h. Centrifuging, washing with 50% (v/v) ethanol water solution for 2 times, washing with deionized water for 2 times, and drying in vacuum drying oven at 50 deg.C for 12 hr. Treating for 3h in a tube furnace at 600 ℃.
(2) 20g of copper powder is added, and ball milling is carried out under the immersion of liquid nitrogen. The weight ratio of the grinding balls to the materials is 15:1, the rotating speed of the ball mill is 20rpm, and the ball milling is carried out for 15 hours.
(3) Drying in a vacuum drying oven at 50 ℃ for 3 h.
(4) And (3) treating for 3h at 200 ℃ in a hydrogen atmosphere to obtain graphene-copper composite powder, namely the graphene-copper composite ultrahigh conductive material.
The compressive yield strength and the resistivity of the obtained composite powder were measured. Compared with comparative examples 1 and 2, the compressive yield strength is improved by 4%, the resistivity is reduced by 16%, and the differences are obvious, wherein P is less than 0.05.
Example 2
A preparation method of a graphene-copper composite ultrahigh conductive material comprises the following steps:
(1) adding 0.1g of copper chloride dihydrate and 0.5g of vitamin C into 25ml of deionized water, adding 40000.01 g of polyethylene glycol, and uniformly stirring. Adding 0.3g of trioctylamine, performing ultrasonic treatment for 20min to obtain milky liquid, adding 0.2g of graphene, performing ultrasonic treatment for 15min, and keeping the temperature in an anticorrosive pressure container at 110 ℃ for 20 h. Centrifuging, washing with 50% (v/v) ethanol water solution for 2 times, washing with deionized water for 2 times, and drying in vacuum drying oven at 50 deg.C for 12 hr. Treating for 3h in a tube furnace at 600 ℃.
(2) 20g of copper powder is added, and ball milling is carried out under the immersion of liquid nitrogen. The weight ratio of the grinding balls to the materials is 20:1, the rotating speed of the ball mill is 20rpm, and the ball milling is carried out for 10 hours.
(3) Drying in a vacuum drying oven at 50 ℃ for 3 h.
(4) And (3) treating for 3h at 200 ℃ in a hydrogen atmosphere to obtain graphene-copper composite powder, namely the graphene-copper composite ultrahigh conductive material.
The compressive yield strength and the resistivity of the obtained composite powder were measured. The compressive yield strength and the resistivity of the obtained composite powder were measured. Compared with example 1, the compressive yield strength and the resistivity are different by less than 2 percent, have no significant difference and P is more than 0.05.
Example 3
A preparation method of a graphene-copper composite ultrahigh conductive material comprises the following steps:
(1) adding 0.1g of copper chloride dihydrate and 0.5g of vitamin C into 25ml of deionized water, adding 40000.01 g of polyethylene glycol, and uniformly stirring. Adding 0.4g of trioctylamine, performing ultrasonic treatment for 15min to obtain milky liquid, adding 0.2g of graphene, performing ultrasonic treatment for 15min, and keeping the temperature in an anticorrosive pressure container at 125 ℃ for 16 h. Centrifuging, washing with 50% (v/v) ethanol water solution for 2 times, washing with deionized water for 2 times, and drying in vacuum drying oven at 60 deg.C for 10 hr. Treating for 3h in a tube furnace at 650 ℃.
(2) 20g of copper powder is added, and ball milling is carried out under the immersion of liquid nitrogen. The weight ratio of the grinding balls to the materials is 15:1, the rotating speed of the ball mill is 20rpm, and the ball milling is carried out for 15 hours.
(3) Drying at 60 deg.C for 3 hr in vacuum drying oven.
(4) And (3) treating for 3h at 220 ℃ in a hydrogen atmosphere to obtain graphene-copper composite powder, namely the graphene-copper composite ultrahigh conductive material.
The compressive yield strength and the resistivity of the obtained composite powder were measured. The compressive yield strength and the resistivity of the obtained composite powder were measured. Compared with example 1, the compressive yield strength and the resistivity are different by less than 2 percent, have no significant difference and P is more than 0.05.
Example 4
A preparation method of a graphene-copper composite ultrahigh conductive material comprises the following steps:
(1) adding 0.1g of copper chloride dihydrate and 0.5g of sodium ascorbyl phosphate into 25ml of deionized water, adding 40000.01 g of polyethylene glycol, and stirring uniformly. Adding 0.4g of 2-hydroxy-5-nonylsalicylaldoxime, performing ultrasonic treatment for 15min to obtain a milky liquid, adding 0.2g of graphene, performing ultrasonic treatment for 15min, and keeping the milky liquid in an anticorrosive pressure container at 125 ℃ for 16 h. Centrifuging, washing with 50% (v/v) ethanol water solution for 2 times, washing with deionized water for 2 times, and drying in vacuum drying oven at 50 deg.C for 12 hr. Treating for 3h in a tube furnace at 600 ℃.
(2) 20g of copper powder is added, and ball milling is carried out under the immersion of liquid nitrogen. The weight ratio of the grinding balls to the materials is 15:1, the rotating speed of the ball mill is 20rpm, and the ball milling is carried out for 15 hours.
(3) Drying in a vacuum drying oven at 50 ℃ for 3 h.
(4) And (3) treating for 3h at 200 ℃ in a hydrogen atmosphere to obtain graphene-copper composite powder, namely the graphene-copper composite ultrahigh conductive material.
The compressive yield strength and the resistivity of the obtained composite powder were measured. Compared with the embodiment 1, the compressive yield strength is improved by 3 percent, and P is less than 0.5; the resistivity is reduced by 11 percent, and P is less than 0.05.
Example 5
The difference between the preparation method of the graphene-copper composite ultrahigh conductive material and the embodiment 1 is that in S11, after the concentration Cs of the surfactant is determined, the concentration of the extractant Ce is determined by the following formula:
wherein, CSAnd Ce in g/100mL, a in the range of 30-50, b in the range of 20-30.
In the method of this embodiment, different strategies are used to determine the concentrations of the extracting agents respectively for different surfactant concentrations. Within the range of Cs, the determined concentration of the extracting agent is proper, a formed liquid phase system can be kept stable for a long time, and graphene and copper particles obtained by reduction are uniformly dispersed.
Example 6
A method for preparing a graphene-copper composite ultra-high conductivity material, which is different from that of example 1, in S11, the high-temperature reaction is performed in a pressure vessel, and the temperature rise of the pressure vessel is controlled by the following PID algorithm:
wherein, the delta u (c) corresponds to the variation of the temperature in the time interval of two testing temperatures; kc is constant, 12-15; f (C) is the deviation at the time of sampling C, f (C-1) is the deviation at the time of sampling C-1, and f (C-2) is the deviation at the time of sampling C-2; t isS1-2s, T, for a sampling periodIIntegration time is 1-1.5 min; t isDThe differential time is 1-1.5 min.
The algorithm for controlling the temperature rise of the pressure container in the embodiment has the advantages of fast temperature rise and small temperature fluctuation amplitude.
In the above examples, the obtained composite powder has uniform graphene distribution as observed by an electron microscope. In XRD, the derived peaks correspond to standard cards of copper one to one. Compared with comparative examples 1 and 2, the products obtained by ball milling have more uniform distribution of graphene.
Comparative example 1
A preparation method of a graphene-copper composite ultrahigh conductive material comprises the following steps:
(1) adding 0.1g of copper chloride dihydrate and 0.5g of vitamin C into 25ml of deionized water, adding 40000.01 g of polyethylene glycol, and uniformly stirring. Adding 0.2g of graphene, carrying out ultrasonic treatment for 30min, and keeping the temperature in an anticorrosive pressure container at 125 ℃ for 16 h. Centrifuging, washing with 50% (v/v) ethanol water solution for 2 times, washing with deionized water for 2 times, and drying in vacuum drying oven at 50 deg.C for 12 hr. Treating for 3h in a tube furnace at 600 ℃.
(2) 20g of copper powder is added, and ball milling is carried out under the immersion of liquid nitrogen. The weight ratio of the grinding balls to the materials is 15:1, the rotating speed of the ball mill is 20rpm, and the ball milling is carried out for 15 hours.
(3) Drying in a vacuum drying oven at 50 ℃ for 3 h.
(4) And (3) treating for 3h at 200 ℃ in a hydrogen atmosphere to obtain graphene-copper composite powder, namely the graphene-copper composite ultrahigh conductive material.
The compressive yield strength and the resistivity of the obtained composite powder were measured.
Comparative example 2
A preparation method of a graphene-copper composite ultrahigh conductive material comprises the following steps:
(1) adding 0.1g of copper chloride dihydrate and 0.5g of vitamin C into 25ml of deionized water, adding 40000.01 g of polyethylene glycol, and uniformly stirring. Adding 0.4g of trioctylamine, performing ultrasonic treatment for 15min to obtain milky liquid, adding 0.2g of graphene, performing ultrasonic treatment for 15min, and keeping the temperature in an anticorrosive pressure container at 125 ℃ for 16 h. Centrifuging, washing with 50% (v/v) ethanol water solution for 2 times, washing with deionized water for 2 times, and drying in vacuum drying oven at 50 deg.C for 12 hr.
(2) 20g of copper powder is added, and ball milling is carried out under the immersion of liquid nitrogen. The weight ratio of the grinding balls to the materials is 15:1, the rotating speed of the ball mill is 20rpm, and the ball milling is carried out for 15 hours.
(3) Drying in a vacuum drying oven at 50 ℃ for 3 h.
(4) And (3) treating for 3h at 200 ℃ in a hydrogen atmosphere to obtain graphene-copper composite powder, namely the graphene-copper composite ultrahigh conductive material.
The compressive yield strength and the resistivity of the obtained composite powder were measured. The compressive yield strength and resistivity were not significantly different from those of comparative example 1.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (8)
1. A preparation method of a graphene-copper composite ultrahigh-conductivity material is characterized by comprising the following steps:
s11, mixing the ionized water with copper salt, a reducing agent and a surfactant, mixing with an extracting agent, mixing with graphene, reacting at high temperature, centrifuging to obtain a solid substance, cleaning, and drying in vacuum;
s12, oxidizing;
s13, mixing the copper powder and ball milling;
s14, vacuum drying;
s15, roasting in a hydrogen atmosphere to obtain graphene-copper composite powder, namely the graphene-copper composite ultrahigh conductive material;
in S11, the weight ratio of the copper salt, the reducing agent, the surfactant, the extracting agent and the graphene is 0.1: (0.4-0.6): (0.005-0.02): (0.3-0.5): (0.1-0.3);
in S11, after the concentration Cs of the surfactant is determined, the concentration of the extractant Ce is determined by the following formula:
wherein, CSAnd Ce in g/100mL, a in the range of 30-50, b in the range of 20-30.
2. The method according to claim 1, wherein in S11, the copper salt is copper chloride dihydrate, the reducing agent is ascorbic acid or sodium ascorbyl phosphate, the surfactant is polyethylene glycol 4000, and the extracting agent is trioctylamine or 2-hydroxy-5-nonylsalicylaldoxime.
3. The method as claimed in claim 1, wherein in S11, the high temperature reaction is maintained at 125 ℃ for 15-20h, and the vacuum drying is performed at 50-60 ℃ for 3-4 h.
4. The method as claimed in claim 1, wherein in S12, the oxidation treatment is carried out at 600-650 ℃ for 3-4 h.
5. The preparation method according to claim 1, wherein in S13, the weight ratio of the grinding balls to the materials is (15-20): 1, the rotation speed of the ball mill is 20-30rpm, and the ball milling is carried out for 10-15 h.
6. The method according to claim 1, wherein in S14, the vacuum drying is performed at 50-60 ℃ for 3-4 h.
7. The method as claimed in claim 1, wherein the calcination temperature in S15 is 200-250 ℃ and the calcination time is 2.5-3 h.
8. The method according to claim 1, wherein the high-temperature reaction is performed in a pressure vessel in S11, and the temperature rise of the pressure vessel is controlled by the following PID algorithm:
wherein, the delta u (c) corresponds to the variation of the temperature in the time interval of two testing temperatures; kc is constant, 12-15; f (C) is the deviation at the time of sampling C, f (C-1) is the deviation at the time of sampling C-1, and f (C-2) is the deviation at the time of sampling C-2; t isS1-2s, T, for a sampling periodIIntegration time is 1-1.5 min; t isDThe differential time is 1-1.5 min.
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