CN107557769A - A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material - Google Patents
A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material Download PDFInfo
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- CN107557769A CN107557769A CN201710619724.8A CN201710619724A CN107557769A CN 107557769 A CN107557769 A CN 107557769A CN 201710619724 A CN201710619724 A CN 201710619724A CN 107557769 A CN107557769 A CN 107557769A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 142
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 123
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 239000011248 coating agent Substances 0.000 title claims abstract description 50
- 238000000576 coating method Methods 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000007747 plating Methods 0.000 claims abstract description 88
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 72
- 239000007788 liquid Substances 0.000 claims abstract description 59
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 40
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 35
- 229910052709 silver Inorganic materials 0.000 claims abstract description 35
- 239000004332 silver Substances 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000007772 electroless plating Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 50
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- 229910000365 copper sulfate Inorganic materials 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- -1 boron Sodium hydride Chemical compound 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 3
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001263 FEMA 3042 Substances 0.000 claims description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000012493 hydrazine sulfate Substances 0.000 claims description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 2
- 229940033123 tannic acid Drugs 0.000 claims description 2
- 235000015523 tannic acid Nutrition 0.000 claims description 2
- 229920002258 tannic acid Polymers 0.000 claims description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims 2
- 229940015043 glyoxal Drugs 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 15
- 238000001035 drying Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000956 alloy Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 11
- UIFOTCALDQIDTI-UHFFFAOYSA-N arsanylidynenickel Chemical compound [As]#[Ni] UIFOTCALDQIDTI-UHFFFAOYSA-N 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229910001961 silver nitrate Inorganic materials 0.000 description 8
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- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 125000002353 D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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Abstract
The present invention relates to a kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, belong to electromagnetic shielding composite material preparing technical field.The present invention sequentially adds nickel-plating carbon nanotube and reducing agent in deionized water, and supersound process obtains nickel-plating carbon nanotube/reducing agent suspending liquid A；Prepare silver ammino solution B or copper-bath C；Nickel-plating carbon nanotube/reducing agent suspending liquid A is well mixed with silver ammino solution B or copper sulphate C solution, electroless plating reaction under the conditions of being 60 ~ 80 DEG C in temperature, the reaction time is controlled to be drying to obtain complex metal layer coating carbon nanotubes electromagnetic shielding material in 20 ~ 40min, separation of solid and liquid, the washing of gained solid.The present invention deposits to form composite in the enterprising row metal of nickel-plating carbon nanotube, improve the electromagnet shield effect of nickel-plating carbon nanotube, reduce when reaching same electromagnetic shield effectiveness using the dosage of composite, the weight of coating for EMI shielding is advantageously reduced, it is had wider application field.
Description
Technical field
The present invention relates to a kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, belong to electromagnetic screen
Cover technical field of composite preparation.
Background technology
With scientific technological advance, various electronic equipments are increasingly popularized in people live, and are pacified caused by electromagnetic wave
Full problem is also increasingly taken seriously.The electromagenetic wave radiation material of carbon nano tube compound material also becomes scholars and studied in recent years
Focus.CNT (CNTs) is since 1991 are found by Iijima, because it has excellent electricity, magnetics and power
Performance is learned, makes it be able to widely study and apply in Field Emission Display, the field such as composite material reinforcement body and conductive material.
In terms of electromagnetic shielding, CNTs also shows excellent performance, and by the metals such as silver, copper, nickel and CNTs or carbon fiber system
Standby composite is in the existing Primary Study in electromagnetic shielding field.But the nano effects of CNTs in itself, make it easily reunite, disperse
Property it is poor, and between CNTs and matrix material be difficult to realize preferable interface cohesion, this largely constrains its application.
The electromagnetic shielding material of present main flow includes silver-colored system, carbon system, copper system and nickel system etc..Although silver system electromagnetic shielding material
Electric conductivity and capability of electromagnetic shielding are excellent, but high cost factor makes it be only used for some special fields；Carbon system applies
Expect poorly conductive, electromagnetic shielding efficiency is low, can only typically be used as antistatic material；Copper system electromagnetic shielding material resistivity is relatively low,
Electric conductivity but because the big problem of its amount of filler makes its application narrower；And there is its electromagnetic parameter in nickel system electromagnetic shielding material
Significant change can be had with frequency, cause its electromagnet shield effect to be optimal.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of complex metal layer coating carbon nanotubes electromagnetic shielding material
Preparation method, i.e., using nickel-plating carbon nanotube as raw material, then with molecular level blend method chemical plating copper or silver, improve its electricity
Magnetic shield performance.
A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, is concretely comprised the following steps：
（1）Nickel-plating carbon nanotube and reducing agent are sequentially added in deionized water, supersound process obtains nickel-plating carbon nanotube/reduction
Agent suspending liquid A；
（2）Prepare silver ammino solution B or copper sulfate solution C；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained silver ammino solution B or copper sulphate
Aqueous solution C is well mixed, 20 ~ 40min of electroless plating reaction under the conditions of being 60 ~ 80 DEG C in temperature, separation of solid and liquid, the washing of gained solid
It is drying to obtain complex metal layer coating carbon nanotubes electromagnetic shielding material；
The step（1）The concentration of nickel-plating carbon nanotube is 15 ~ 30g/L in middle nickel-plating carbon nanotube/reducing agent suspending liquid A, also
The concentration of former agent is 5 ~ 10g/L；
The step（1）Middle reducing agent is hydrazine hydrate, formaldehyde, D-glucose, sodium potassium tartrate tetrahydrate, hydrazine sulfate, ethylenediamine, second two
Aldehyde, sodium borohydride, aldolactol, triethanolamine, glycerine, tannic acid or Mitouer；
The step（2）Ag (NH in silver ammino solution B3)2OH concentration is 10 ~ 12g/L, copper sulphate in copper sulfate solution C
Concentration is 15 ~ 25g/L；
The step（3）Nickel-plating carbon nanotube/reducing agent suspending liquid A and silver ammino solution B volume ratio are 1:(1 ~ 3), nickel-plated carbon
Nanotube/reducing agent suspending liquid A and copper sulfate solution C volume ratio are 1:(1~3)；
According to patent 201610868742.5, " a kind of carbon nano tube surface uniformly coats the side of argent to the nickel-plating carbon nanotube
The method that ullrasonic spraying is silver-plated in method and device " carries out ullrasonic spraying nickel plating, and the purity of nickel-plating carbon nanotube is 95 ~ 99.9%；
Beneficial effects of the present invention：
（1）The inventive method is simple, safe and reliable, equipment is simple, is easily achieved industrialization；
（2）The present invention, as raw material, can improve CNT and metallic copper or the interface cohesion of silver using nickel-plating carbon nanotube
The problem of dispersed in the base, more forming core sites can be provided for the formation of follow-up composite deposite, it is favourable compound
The formation of coating.
Brief description of the drawings
Fig. 1 is the composition metal nickeline coating carbon nanotubes that the embodiment of the present invention 1 obtains and the compound gold that embodiment 5 obtains
Belong to the capability of electromagnetic shielding curve map of ambrose alloy coating carbon nanotubes；
Fig. 2 is the TEM figures for the composition metal nickeline coating carbon nanotubes that the embodiment of the present invention 1 obtains；
Fig. 3 is the TEM figures for the composition metal ambrose alloy coating carbon nanotubes that the embodiment of the present invention 5 obtains.
Embodiment
The present invention is described in further detail with reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1：A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, is concretely comprised the following steps：
（1）By nickel-plating carbon nanotube and reducing agent（Reducing agent is hydrazine hydrate）Sequentially add in deionized water, be ultrasonically treated 30min
Nickel-plating carbon nanotube/reducing agent suspending liquid A is obtained, nickel-plating carbon nanotube wherein in nickel-plating carbon nanotube/reducing agent suspending liquid A
Concentration is 15g/L, reducing agent（Hydrazine hydrate）Concentration be 5g/L；
（2）Ammoniacal liquor to the silver nitrate that mass fraction is 25% is added in the silver nitrate suspension that 100mL concentration is 15g/L to suspend
Liquid is clarified, then the NaOH solution for being 5mol/L with concentration adjusts pH value to obtaining silver ammino solution B after 10, Ag in silver ammino solution B
(NH3)2OH concentration is 10g/L；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained silver ammino solution B is well mixed,
The volume ratio of wherein nickel-plating carbon nanotube/reducing agent suspending liquid A and silver ammino solution B is 1:1, chemistry under the conditions of being 60 DEG C in temperature
Plating reaction 20min, separation of solid and liquid, the washing of gained solid are drying to obtain complex metal layer coating carbon nanotubes electromagnetic shielding material
（Nickeline complex metal layer enveloped carbon nanometer tube）；
Complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Nickeline complex metal layer carbon coated nanometer
Pipe）TEM figures as shown in Fig. 2 as can be seen from Figure 2, the silver coating of nickel-plating carbon nanotube is mainly wrapped in carbon with Argent grain shape and received
There is not the phenomenon reunited in the surface of mitron, nickel-plating carbon nanotube；
Complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Nickeline complex metal layer carbon coated nanometer
Pipe）Capability of electromagnetic shielding curve as shown in figure 1, from fig. 1, it can be seen that under 8.2~12.4GHz frequencies, different composite powder pressure
At different frequencies, it is electromagnetically shielded, and rule is basically identical for piece sample, because the electrical conductivity of silver is of a relatively high, and relative permeability
It is relatively low, make the capability of electromagnetic shielding of its composite granule mainly by reflection loss.
Embodiment 2：A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, is concretely comprised the following steps：
（1）By nickel-plating carbon nanotube and reducing agent（Reducing agent is formaldehyde）Sequentially add in deionized water, be ultrasonically treated 30min and obtain
To nickel-plating carbon nanotube/reducing agent suspending liquid A, nickel-plating carbon nanotube is dense wherein in nickel-plating carbon nanotube/reducing agent suspending liquid A
Spend for 20g/L, the concentration of reducing agent is 10g/L；
（2）Ammoniacal liquor to the silver nitrate that mass fraction is 25% is added in the silver nitrate suspension that 100mL concentration is 20g/L to suspend
Liquid is clarified, then the NaOH solution for being 5mol/L with concentration adjusts pH value to obtaining silver ammino solution B after 10, Ag in silver ammino solution B
(NH3)2OH concentration is 11 g/L；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained silver ammino solution B is well mixed,
The volume ratio of wherein nickel-plating carbon nanotube/reducing agent suspending liquid A and silver ammino solution B is 1:2, chemistry under the conditions of being 70 DEG C in temperature
Plating reaction 30min, separation of solid and liquid, the washing of gained solid are drying to obtain complex metal layer coating carbon nanotubes electromagnetic shielding material
（Nickeline complex metal layer enveloped carbon nanometer tube）；
From complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Nickeline complex metal layer carbon coated is received
Mitron）TEM figures understand that the silver coating of nickel-plating carbon nanotube is mainly the surface that CNT is wrapped in Argent grain shape, plating
There is not the phenomenon reunited in nickel CNT.
Embodiment 3：A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, is concretely comprised the following steps：
（1）By nickel-plating carbon nanotube and reducing agent（Reducing agent is sodium potassium tartrate tetrahydrate）Sequentially add in deionized water, be ultrasonically treated
30min obtains nickel-plating carbon nanotube/reducing agent suspending liquid A, and wherein nickel-plated carbon is received in nickel-plating carbon nanotube/reducing agent suspending liquid A
The concentration of mitron is 25g/L, and the concentration of reducing agent is 10g/L；
（2）Ammoniacal liquor to the silver nitrate that mass fraction is 25% is added in the silver nitrate suspension that 100mL concentration is 20g/L to suspend
Liquid is clarified, then the NaOH solution for being 5mol/L with concentration adjusts pH value to obtaining silver ammino solution B after 10, Ag in silver ammino solution B
(NH3)2OH concentration is 12g/L；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained silver ammino solution B is well mixed,
The volume ratio of wherein nickel-plating carbon nanotube/reducing agent suspending liquid A and silver ammino solution B is 1:3, chemistry under the conditions of being 70 DEG C in temperature
Plating reaction 40min, separation of solid and liquid, the washing of gained solid are drying to obtain complex metal layer coating carbon nanotubes electromagnetic shielding material
（Nickeline complex metal layer enveloped carbon nanometer tube）；
From complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Nickeline complex metal layer carbon coated is received
Mitron）TEM figures understand that the silver coating of nickel-plating carbon nanotube is mainly the surface that CNT is wrapped in Argent grain shape, plating
There is not the phenomenon reunited in nickel CNT.
Embodiment 4：A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, is concretely comprised the following steps：
（1）By nickel-plating carbon nanotube and reducing agent（Reducing agent is glycerine）Sequentially add in deionized water, be ultrasonically treated 30min
Nickel-plating carbon nanotube/reducing agent suspending liquid A is obtained, nickel-plating carbon nanotube wherein in nickel-plating carbon nanotube/reducing agent suspending liquid A
Concentration is 30g/L, and the concentration of reducing agent is 10g/L；
（2）Ammoniacal liquor to the silver nitrate that mass fraction is 25% is added in the silver nitrate suspension that 100mL concentration is 25g/L to suspend
Liquid is clarified, then the NaOH solution for being 5mol/L with concentration adjusts pH value to obtaining silver ammino solution B after 10, Ag in silver ammino solution B
(NH3)2OH concentration is 12g/L；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained silver ammino solution B is well mixed,
The volume ratio of wherein nickel-plating carbon nanotube/reducing agent suspending liquid A and silver ammino solution B is 1:3, chemistry under the conditions of being 80 DEG C in temperature
Plating reaction 40min, separation of solid and liquid, the washing of gained solid are drying to obtain complex metal layer coating carbon nanotubes electromagnetic shielding material
（Nickeline complex metal layer enveloped carbon nanometer tube）；
From complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Nickeline complex metal layer carbon coated is received
Mitron）TEM figures understand that the silver coating of nickel-plating carbon nanotube is mainly the surface that CNT is wrapped in Argent grain shape, plating
There is not the phenomenon reunited in nickel CNT.
Embodiment 5：A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, is concretely comprised the following steps：
（1）By nickel-plating carbon nanotube and reducing agent（Reducing agent is hydrazine hydrate）Sequentially add in deionized water, be ultrasonically treated 30min
Nickel-plating carbon nanotube/reducing agent suspending liquid A is obtained, nickel-plating carbon nanotube wherein in nickel-plating carbon nanotube/reducing agent suspending liquid A
Concentration is 15g/L, and the concentration of reducing agent is 5g/L；
（2）Copper sulphate is dissolved into deionized water and is configured to copper sulfate solution C, copper sulphate in wherein copper sulfate solution C
Concentration be 10g/L；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained copper sulfate solution C is mixed
Uniformly, the volume ratio of wherein nickel-plating carbon nanotube/reducing agent suspending liquid A and copper sulfate solution C is 1:1, it is 60 DEG C in temperature
Under the conditions of electroless plating reaction 20min, separation of solid and liquid, gained solid washing be drying to obtain complex metal layer coating carbon nanotubes electromagnetism
Shielding material（Ambrose alloy complex metal layer enveloped carbon nanometer tube）；
Complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Ambrose alloy complex metal layer carbon coated nanometer
Pipe）TEM figures as shown in figure 3, as can be seen from Figure 3, the copper plate of nickel-plating carbon nanotube is mainly wrapped in carbon with copper graininess and received
The surface of mitron, there is not the phenomenon reunited in nickel-plating carbon nanotube, and is coated by copper particle, forms composite deposite；
Complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Ambrose alloy complex metal layer carbon coated nanometer
Pipe）Capability of electromagnetic shielding curve as shown in figure 1, from fig. 1, it can be seen that under 8.2~12.4GHz frequencies, different composite powder pressure
At different frequencies, it is basically identical that it is electromagnetically shielded rule to piece sample.Because the electrical conductivity of copper is of a relatively high, and relative permeability
It is relatively low, make the capability of electromagnetic shielding of its composite granule mainly by reflection loss.
Embodiment 6：A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, is concretely comprised the following steps：
（1）By nickel-plating carbon nanotube and reducing agent（Reducing agent is sodium borohydride）Sequentially add in deionized water, be ultrasonically treated
30min obtains nickel-plating carbon nanotube/reducing agent suspending liquid A, and wherein nickel-plated carbon is received in nickel-plating carbon nanotube/reducing agent suspending liquid A
The concentration of mitron is 20g/L, and the concentration of reducing agent is 10g/L；
（2）Copper sulphate is dissolved into deionized water and is configured to copper sulfate solution C, copper sulphate in wherein copper sulfate solution C
Concentration be 15g/L；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained copper sulfate solution C is mixed
Uniformly, the volume ratio of wherein nickel-plating carbon nanotube/reducing agent suspending liquid A and copper sulfate solution C is 1:2, it is 70 DEG C in temperature
Under the conditions of electroless plating reaction 30min, separation of solid and liquid, gained solid washing be drying to obtain complex metal layer coating carbon nanotubes electromagnetism
Shielding material（Ambrose alloy complex metal layer enveloped carbon nanometer tube）；
From complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Ambrose alloy complex metal layer carbon coated is received
Mitron）TEM figures understand that the copper plate of nickel-plating carbon nanotube is mainly the surface that CNT is wrapped in copper graininess, plating
There is not the phenomenon reunited in nickel CNT, and is coated by copper particle, forms composite deposite.
Embodiment 7：A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, is concretely comprised the following steps：
（1）By nickel-plating carbon nanotube and reducing agent（Reducing agent is formaldehyde）Sequentially add in deionized water, be ultrasonically treated 30min and obtain
To nickel-plating carbon nanotube/reducing agent suspending liquid A, nickel-plating carbon nanotube is dense wherein in nickel-plating carbon nanotube/reducing agent suspending liquid A
Spend for 25g/L, the concentration of reducing agent is 7.5g/L；
（2）Copper sulphate is dissolved into deionized water and is configured to copper sulfate solution C, copper sulphate in wherein copper sulfate solution C
Concentration be 20g/L；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained copper sulfate solution C is mixed
Uniformly, the volume ratio of wherein nickel-plating carbon nanotube/reducing agent suspending liquid A and copper sulfate solution C is 1:3, it is 70 DEG C in temperature
Under the conditions of electroless plating reaction 40min, separation of solid and liquid, gained solid washing be drying to obtain complex metal layer coating carbon nanotubes electromagnetism
Shielding material（Ambrose alloy complex metal layer enveloped carbon nanometer tube）；
From complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Ambrose alloy complex metal layer carbon coated is received
Mitron）TEM figures understand that the copper plate of nickel-plating carbon nanotube is mainly the surface that CNT is wrapped in copper graininess, plating
There is not the phenomenon reunited in nickel CNT, and is coated by copper particle, forms composite deposite.
Embodiment 8：A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, is concretely comprised the following steps：
（1）By nickel-plating carbon nanotube and reducing agent（Reducing agent is D-glucose）Sequentially add in deionized water, be ultrasonically treated
30min obtains nickel-plating carbon nanotube/reducing agent suspending liquid A, and wherein nickel-plated carbon is received in nickel-plating carbon nanotube/reducing agent suspending liquid A
The concentration of mitron is 30g/L, and the concentration of reducing agent is 10g/L；
（2）Copper sulphate is dissolved into deionized water and is configured to copper sulfate solution C, copper sulphate in wherein copper sulfate solution C
Concentration be 25g/L；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained copper sulfate solution C is mixed
Uniformly, the volume ratio of wherein nickel-plating carbon nanotube/reducing agent suspending liquid A and copper sulfate solution C is 1:3, it is 80 DEG C in temperature
Under the conditions of electroless plating reaction 40min, separation of solid and liquid, gained solid washing be drying to obtain complex metal layer coating carbon nanotubes electromagnetism
Shielding material（Ambrose alloy complex metal layer enveloped carbon nanometer tube）；
From complex metal layer coating carbon nanotubes electromagnetic shielding material manufactured in the present embodiment（Ambrose alloy complex metal layer carbon coated is received
Mitron）TEM figures understand that the copper plate of nickel-plating carbon nanotube is mainly the surface that CNT is wrapped in copper graininess, plating
There is not the phenomenon reunited in nickel CNT, and is coated by copper particle, forms composite deposite.
Claims (5)
1. a kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material, it is characterised in that concretely comprise the following steps：
（1）Nickel-plating carbon nanotube and reducing agent are sequentially added in deionized water, supersound process obtains nickel-plating carbon nanotube/reduction
Agent suspending liquid A；
（2）Prepare silver ammino solution B or copper sulfate solution C；
（3）By step（1）Gained nickel-plating carbon nanotube/reducing agent suspending liquid A and step（2）Gained silver ammino solution B or copper sulphate
Aqueous solution C is well mixed, 20 ~ 40m of electroless plating reaction under the conditions of being 60 ~ 80 DEG C in temperature, separation of solid and liquid, and the washing of gained solid is dry
It is dry to produce complex metal layer coating carbon nanotubes electromagnetic shielding material.
2. the preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material according to claim 1, its feature exists
In：Step（1）The concentration of nickel-plating carbon nanotube is 15 ~ 30g/L in middle nickel-plating carbon nanotube/reducing agent suspending liquid A, reducing agent
Concentration is 5 ~ 10g/L.
3. the preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material according to claim 1, its feature exists
In：Step（1）Middle reducing agent is hydrazine hydrate, formaldehyde, D-glucose, sodium potassium tartrate tetrahydrate, hydrazine sulfate, ethylenediamine, glyoxal, boron
Sodium hydride, aldolactol, triethanolamine, glycerine, tannic acid or Mitouer.
4. the preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material according to claim 1, its feature exists
In：Step（2）Ag (NH in silver ammino solution B3)2OH concentration is 10 ~ 12g/L, and the concentration of copper sulphate is in copper sulfate solution C
15~25 g/L。
5. the preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material according to claim 1, its feature exists
In：Step（3）Nickel-plating carbon nanotube/reducing agent suspending liquid A and silver ammino solution B volume ratio are 1:(1 ~ 3), nickel-plated carbon nanometer
Pipe/reducing agent suspending liquid A and copper sulfate solution C volume ratio are 1:(1~3).
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| CN110746740A (en) * | 2019-10-21 | 2020-02-04 | 暨南大学 | PEEK electromagnetic shielding material and preparation method and application thereof |
| CN112888287A (en) * | 2021-01-12 | 2021-06-01 | 无锡东恒新能源科技有限公司 | Preparation method of electromagnetic shielding material |
| CN115491665A (en) * | 2022-09-16 | 2022-12-20 | 西南科技大学 | Chemical copper plating process for super-ordered carbon nanotube film and application thereof |
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