CN114700490A - Preparation method of nickel-coated graphite composite particles and application of nickel-coated graphite composite particles in electromagnetic shielding field - Google Patents
Preparation method of nickel-coated graphite composite particles and application of nickel-coated graphite composite particles in electromagnetic shielding field Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 101
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 86
- 239000010439 graphite Substances 0.000 title claims abstract description 86
- 239000011246 composite particle Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000007747 plating Methods 0.000 claims abstract description 81
- 239000000126 substance Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims abstract description 19
- 239000001509 sodium citrate Substances 0.000 claims abstract description 19
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims abstract description 19
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 17
- 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 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940074439 potassium sodium tartrate Drugs 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 238000010438 heat treatment Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- 239000011159 matrix material Substances 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 11
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 7
- 239000004945 silicone rubber Substances 0.000 claims description 6
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 206010070834 Sensitisation Diseases 0.000 abstract description 4
- 238000001994 activation Methods 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 230000008313 sensitization Effects 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 9
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
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- Chemically Coating (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of nickel-coated graphite composite particles and application of the nickel-coated graphite composite particles in the field of electromagnetic shielding, and belongs to the technical field of preparation of electromagnetic wave shielding materials. According to the invention, the purpose of stabilizing the chemical nickel plating reaction rate is achieved by adjusting the content ratio of the potassium sodium tartrate complexing agent to the sodium citrate complexing agent, a nickel coating with high conductive path, high adhesive force and low internal stress is obtained after the reaction, and the problems of loose coating, poor stability of plating solution and the like caused by uncontrollable reaction rate in the chemical nickel plating process are avoided. Meanwhile, hydrazine hydrate is used as a reducing agent to obtain a pure nickel coating, so that the problems of poor electromagnetic performance and the like caused by the formation of an amorphous coating containing impurity elements such as phosphorus, boron and the like in the prior art are solved. In addition, the traditional sensitization activation process is omitted, the preparation process is simple, the period is short, the cost is low, the product performance is excellent, and a set of feasible new scheme is provided for promoting the industrial production and application of the nickel-coated graphite composite particles with multiple specifications and high quality.
Description
Technical Field
The invention belongs to the technical field of preparation of electromagnetic wave shielding materials, and particularly relates to a preparation method of nickel-coated graphite composite particles and application of the nickel-coated graphite composite particles in the field of electromagnetic shielding.
Background
Various electronic devices are widely used in daily life, so that the user can conveniently and efficiently use and experience the electronic devices, and meanwhile, electromagnetic waves with various frequencies and wavelengths are continuously radiated outwards, and serious electromagnetic wave pollution is caused. This not only interferes with some sensitive electronic devices and affects their normal operation, but also causes irreversible damage to the human body and other living beings. Therefore, a high-performance electromagnetic wave shielding material is a new material for solving such problems.
In recent years, due to the excellent electric conduction and magnetic conduction performance of the metal nickel, the performance requirement of potential application of the electromagnetic wave shielding material is met, and the nickel has good oxidation resistance and can be suitable for outdoor, high-temperature and other multi-application scenes. The nickel-coated graphite composite particles obtained by compounding the metallic nickel and the flaky graphite with the super-large diameter-thickness ratio have the excellent performances of two materials, such as high conductivity, small density, good lubricity and the like. Therefore, the nickel-coated graphite composite particles are increasingly and widely concerned as electromagnetic wave shielding materials, and have wide application prospects.
However, the existing preparation of nickel-coated graphite composite particles has the problems of poor controllability of reaction process, high production cost, complex preparation process, serious environmental pollution and the like, and the mass production of the composite particles is limited. If the chemical plating is carried out by adopting a single complexing agent plating solution, the reaction rate is too high, so that the internal stress of a nickel shell is large, and the product quality is poor; in addition, expensive reagents of stannous chloride and palladium chloride are mostly used in the sensitization activation process before the traditional chemical plating, so that the preparation cost of the composite particles is increased, and the commercial popularization is difficult to realize; the nickel-coated graphite composite particles prepared by the in-situ generation method by utilizing the autocatalysis of nickel have the defects of long preparation period and complicated production process.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of nickel-coated graphite composite particles and application of the nickel-coated graphite composite particles in the field of electromagnetic shielding. The method adopts a double-complexing agent nickel plating solution in the chemical nickel plating process, and achieves the purpose of stabilizing the reaction rate of the chemical nickel plating by adjusting the content ratio of two complexing agents, namely potassium sodium tartrate and sodium citrate; further ensuring that a nickel coating with high conductive path, high adhesive force and low internal stress is obtained after the reaction, and avoiding the problems of loose coating, poor stability of plating solution and the like caused by uncontrollable reaction rate in the chemical nickel plating process. Meanwhile, hydrazine hydrate is used as a reducing agent to obtain a pure nickel coating, so that the problems of poor electromagnetic performance and the like caused by the formation of an amorphous coating containing impurity elements such as phosphorus, boron and the like in the prior art are solved. In addition, the invention omits the traditional sensitization activation process, and has simple preparation process, short period and low cost.
The technical scheme adopted by the invention is as follows:
a preparation method of nickel-coated graphite composite particles comprises the following steps:
step 1: placing the flaky graphite matrix in a sodium hydroxide solution for heating and stirring to finish oil removal cleaning pretreatment, and then placing the flaky graphite matrix in a vacuum drying box for drying for later use;
step 2: preparing a chemical nickel plating solution, and adjusting the pH value of the nickel plating solution to 11-13 by using a sodium hydroxide solution. The nickel plating solution comprises the following components: nickel sulfate, sodium potassium tartrate, sodium citrate and hydrazine hydrate.
And step 3: and (3) placing the graphite substrate to be used in the step (1) into the nickel plating solution prepared in the step (2) for chemical plating under the condition of heating and stirring.
And 4, step 4: and after the chemical plating reaction is finished, carrying out suction filtration and cleaning on the obtained composite particles, and placing the composite particles in a vacuum drying box for drying to obtain the nickel-coated graphite composite particles.
Further, the particle size of the flaky graphite in the step 1 is 40-200 μm, the concentration of the sodium hydroxide solution is 75-120 g/L, the stirring and heating temperature is 50-70 ℃, the stirring time is 20-60 min, the vacuum drying temperature is 30-80 ℃, and the drying time is 12-24 h.
Further, in the step 2, the mass concentrations of the components of the nickel plating solution are respectively as follows: 16-47 g/L of nickel sulfate, 9.4-24 g/L of sodium potassium tartrate, 23.5-96 g/L of sodium citrate and 10-25 ml/L of 80 wt.% hydrazine hydrate; the specific concentration of the sodium hydroxide is determined by the pH value of the nickel plating solution; the mass ratio of the potassium sodium tartrate to the sodium citrate is 1: 2.5-4.
Further, in the step 3, the heating temperature is 75-90 ℃, the addition amount of the graphite matrix is 0.5-5 g/L, and the chemical plating time is 40-90 min.
Further, in the step 4, the temperature of vacuum drying is 30-50 ℃, and the drying time is 5-8 h.
The nickel-coated graphite composite particles obtained by the preparation method are applied to the field of electromagnetic wave shielding, the nickel-coated graphite composite particles are mixed with solvents such as organic silicon oil and the like to prepare a conductive shielding silicone rubber sheet with the thickness of 0.5-2 mm, and the electromagnetic wave shielding performance of the conductive shielding silicone rubber sheet in a 5.85-26.5 GHz band is tested by adopting a waveguide method.
Compared with the prior art, the invention has the beneficial effects that:
1. the reaction process has strong controllability. By regulating and controlling the adding proportion of the two complexing agents in the plating solution, the reaction of chemical nickel plating is effectively improved, so that a nickel plating layer with a high conductive path, high adhesive force and low internal stress is obtained after the reaction, and a prerequisite condition is provided for obtaining the organic silicon rubber with ultrahigh shielding efficiency.
2. The process flow is simple, and the preparation cost is low. The traditional sensitization and activation process for preparing the nickel-coated graphite composite particles by chemical plating is omitted, and the cleaned and deoiled graphite matrix is directly subjected to chemical nickel plating, so that the preparation period of the powder is greatly shortened, and the preparation cost of the powder is reduced.
3. The plating layer does not contain impurity elements such as phosphorus, boron and the like. The pure nickel plating layer is obtained after the graphite matrix is chemically plated, the pure nickel plating layer has the characteristics of high conductivity, good oxidation resistance and the like, and the further prepared conductive shielding silicone rubber sheet has excellent high-frequency electromagnetic wave shielding performance, and the electromagnetic wave shielding efficiency can reach 108.5dB at a wave band of 5.85-26.5 GHz.
4. The preparation process is green and environment-friendly. Hydrazine hydrate is selected as a reducing agent, and reaction products are nitrogen and water, so that the method is green and pollution-free and is suitable for batch production.
Drawings
FIG. 1 is an X-ray diffraction pattern of nickel-coated graphite composite particles according to example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the nickel-coated graphite composite particle in example 1 of the present invention;
FIG. 3 is an elemental characterization image of nickel-coated graphite composite particles according to example 1 of the present invention; wherein, (a) is a single composite particle scanning electron microscope image, (b) is a carbon element distribution characterization image, and (c) is a nickel element distribution characterization image;
FIG. 4 is a graph showing the electromagnetic wave shielding effectiveness of the nickel-coated graphite composite particle in example 1 of the present invention;
FIG. 5 is an X-ray diffraction pattern of the nickel-coated graphite composite particle in comparative example 1;
FIG. 6 is a scanning electron microscope image of the nickel-coated graphite composite particle in comparative example 1;
FIG. 7 is a scanning electron microscope image of the composite particle in comparative example 2;
fig. 8 is a scanning electron microscope image of the composite particle in comparative example 3.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for purposes of comparison and explanation only, and the present invention is not limited to these examples. It should be noted that all other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
Example 1
A preparation method of nickel-coated graphite composite particles comprises the following specific implementation steps:
step 1: 1g of scaly graphite matrix with the particle size of 100 mu m is placed in 500ml of sodium hydroxide solution with the concentration of 80g/L for heating and stirring, the heating temperature is 50 ℃, and the stirring time is 30 min. Finishing oil removal cleaning pretreatment, and then placing the mixture in a vacuum drying box at 40 ℃ for drying for 12h for later use;
step 2: preparing chemical nickel plating solution, and adjusting the pH value of the plating solution to 12 by using sodium hydroxide solution. The concentration of nickel sulfate in the plating solution is 16g/L, the concentration of potassium sodium tartrate is 9.4g/L, the concentration of sodium citrate is 23.5g/L, the concentration of hydrazine hydrate is 10g/L, and the adding amount mass ratio of potassium sodium tartrate to sodium citrate in the embodiment is 1: 2.5.
And step 3: and (3) placing the graphite substrate to be used in the step (1) into the nickel plating solution prepared in the step (2) for chemical plating under the conditions of heating and stirring, wherein the heating temperature is 80 ℃, the addition amount of the graphite substrate is 0.5g/L, and the chemical plating time is about 43 min.
And 4, step 4: and after the chemical plating reaction is finished, carrying out suction filtration and cleaning on the obtained composite particles, and then placing the composite particles in a vacuum drying box for drying at the drying temperature of 30 ℃ for 7 hours to obtain the nickel-coated graphite composite particles.
The XRD pattern of the obtained nickel-coated graphite composite particle is shown in fig. 1, and contains only diffraction peaks of graphite and nickel. The microstructure is shown in FIG. 2, and can be seen as a sheet structure with a compact shell layer. The corresponding elemental analysis chart of the nickel plating surface is shown in fig. 3, and nickel particles are densely and uniformly distributed on the surface of the graphite matrix. The prepared nickel-coated graphite composite particles are mixed with other solvents such as organic silicon oil and the like to prepare a conductive shielding silicone rubber sheet with the thickness of 1mm, an electromagnetic wave shielding performance test is carried out by adopting a waveguide method, and the measured shielding effectiveness is shown in figure 4 and is stabilized at about 105dB and can reach 108.5dB at J, X, P and K four wave bands.
Example 2
A preparation method of nickel-coated graphite composite particles comprises the following specific implementation steps:
step 1: 1.5g of flaky graphite matrix with the particle size of 100 mu m is placed in 500ml of sodium hydroxide solution with the concentration of 100g/L for heating and stirring, the heating temperature is 60 ℃, and the stirring time is 45 min. The graphite matrix is subjected to oil removal cleaning pretreatment, and then is placed in a vacuum drying box at 60 ℃ to be dried for 16 hours for standby;
step 2: preparing chemical nickel plating solution, and adjusting the pH value of the plating solution to 12.5 by using sodium hydroxide solution. The concentration of nickel sulfate in the plating solution is 20g/L, the concentration of potassium sodium tartrate is 15g/L, the concentration of sodium citrate is 52.5g/L, the concentration of hydrazine hydrate is 15g/L, and the adding amount mass ratio of potassium sodium tartrate to sodium citrate in the embodiment is 1: 3.5.
And 3, step 3: and (3) under the conditions of heating and stirring, placing the graphite substrate to be used in the step (1) into the nickel plating solution prepared in the step (2) for chemical plating, wherein the heating temperature is 85 ℃, the addition amount of the graphite substrate is 2g/L, and the chemical plating time is about 68 min.
And 4, step 4: after the chemical plating reaction is finished, carrying out suction filtration and cleaning on the obtained composite particles, and then placing the composite particles in a vacuum drying oven for drying at the drying temperature of 40 ℃ for 6 hours to obtain the nickel-coated graphite composite particles.
Example 3
A preparation method of nickel-coated graphite composite particles comprises the following specific implementation steps:
step 1: the scaly graphite matrix with the grain diameter of 150 mu m is placed in 500ml of sodium hydroxide solution with the concentration of 95g/L for heating and stirring, the heating temperature is 70 ℃, and the stirring time is 45 min. Finishing oil removal cleaning pretreatment, and then placing the mixture in a vacuum drying box at 60 ℃ for drying for 16h for later use;
step 2: preparing chemical nickel plating solution, and adjusting the pH value of the plating solution to 13 by using sodium hydroxide solution. The concentration of nickel sulfate in the plating solution is 45g/L, the concentration of potassium sodium tartrate is 24g/L, the concentration of sodium citrate is 96g/L, the concentration of hydrazine hydrate is 22g/L, and the mass ratio of the potassium sodium tartrate to the sodium citrate in the embodiment is 1: 4.
And step 3: and (3) under the conditions of heating and stirring, placing the graphite substrate to be used in the step (1) into the nickel plating solution prepared in the step (2) for chemical plating, wherein the heating temperature is 90 ℃, the addition amount of the graphite substrate is 0.5g/L, and the chemical plating time is about 76 min.
And 4, step 4: and after the chemical plating reaction is finished, carrying out suction filtration and cleaning on the obtained composite particles, and then placing the composite particles in a vacuum drying box for drying at the drying temperature of 50 ℃ for 8 hours to obtain the nickel-coated graphite composite particles.
Comparative example 1
A preparation method of nickel-coated graphite composite particles comprises the following specific implementation steps:
step 1: 1g of scaly graphite matrix with the particle size of 100 mu m is placed in a sodium hydroxide solution with the concentration of 80g/L for heating and stirring, the heating temperature is 50 ℃, and the stirring time is 30 min. Finishing oil removal cleaning pretreatment, and then placing the mixture in a vacuum drying box at 40 ℃ for drying for 12h for later use;
and 2, step: preparing chemical nickel plating solution, and adjusting the pH value of the plating solution to 12 by using sodium hydroxide solution. The concentration of nickel sulfate in the plating solution is 16g/L, the concentration of sodium citrate is 32.9g/L, the concentration of hydrazine hydrate is 10g/L, and potassium sodium tartrate is not added in the comparative example.
And step 3: and (3) under the conditions of heating and stirring, placing the graphite substrate to be used in the step (1) into the nickel plating solution prepared in the step (2) for chemical plating, wherein the heating temperature is 80 ℃, the addition amount of the graphite substrate is 0.5g/L, and the chemical plating time is about 26 min.
And 4, step 4: and after the chemical plating reaction is finished, carrying out suction filtration and cleaning on the obtained composite particles, and then placing the composite particles in a vacuum drying box for drying at the drying temperature of 50 ℃ for 8 hours to obtain the nickel-coated graphite composite particles.
The XRD pattern of the obtained nickel-coated graphite composite particle is shown in fig. 5, still only including the diffraction peaks of graphite and nickel, but the diffraction intensity of the nickel peak is significantly reduced compared to the XRD characterization pattern corresponding to example 1, indicating that the crystallinity of the formed nickel particle is reduced. The microstructure is shown in fig. 6, because the reaction rate is too fast, the nickel particles are distributed on the surface of the graphite matrix in a loose manner, and the formed nickel particles are observed to be coarse and not densely arranged.
Comparative example 2
A preparation method of nickel-coated graphite composite particles comprises the following specific implementation steps:
step 1: the scaly graphite matrix with the grain diameter of 100 mu m is placed in a sodium hydroxide solution with the concentration of 100g/L for heating and stirring, the heating temperature is 60 ℃, and the stirring time is 45 min. Finishing oil removal cleaning pretreatment, and then placing the mixture in a vacuum drying box at 60 ℃ for drying for 16h for later use;
step 2: preparing chemical nickel plating solution, and adjusting the pH value of the plating solution to 12.5 by using sodium hydroxide solution. The concentration of nickel sulfate in the plating solution is 20g/L, the concentration of ammonium chloride is 15g/L, the concentration of sodium citrate is 52.5g/L, and the concentration of hydrazine hydrate is 15g/L, wherein in the comparative example, ammonium chloride is used as a complexing agent to replace sodium potassium tartrate and is matched with sodium citrate.
And step 3: and (3) under the conditions of heating and stirring, placing the graphite substrate to be used in the step (1) into the nickel plating solution prepared in the step (2) for chemical plating, wherein the heating temperature is 90 ℃, the addition amount of the graphite substrate is 0.5g/L, and the chemical plating reaction phenomenon is weak.
And 4, step 4: and after the chemical plating reaction is finished, carrying out suction filtration and cleaning on the obtained composite particles, and then placing the composite particles in a vacuum drying box for drying at the drying temperature of 40 ℃ for 6 hours to obtain the nickel-coated graphite composite particles.
The microscopic morphology of the obtained composite particles is shown in fig. 7, and the surface of the graphite matrix only contains sporadic nickel particles, which shows that the plating solution formed by matching the ammonium chloride complexing agent and the sodium citrate complexing agent in the comparative example does not have the capacity of forming a compact nickel shell layer on the surface of the graphite.
Comparative example 3
A preparation method of nickel-coated graphite composite particles comprises the following specific implementation steps:
step 1: the scaly graphite matrix with the grain diameter of 100 mu m is placed in a sodium hydroxide solution with the concentration of 100g/L for heating and stirring, the heating temperature is 60 ℃, and the stirring time is 45 min. Finishing oil removal cleaning pretreatment, and then placing the mixture in a vacuum drying box at 60 ℃ for drying for 16h for later use;
step 2: preparing chemical nickel plating solution, and adjusting the pH value of the plating solution to 12.5 by using sodium hydroxide solution. The concentration of nickel sulfate in the plating solution is 20g/L, the concentration of potassium sodium tartrate is 15g/L, the concentration of ammonium chloride is 52.5g/L, and the concentration of hydrazine hydrate is 15g/L, wherein in the comparative example, ammonium chloride is used as a complexing agent to replace sodium citrate and is matched with the potassium sodium tartrate for use.
And 3, step 3: and (3) under the conditions of heating and stirring, placing the graphite substrate to be used in the step (1) into the nickel plating solution prepared in the step (2) for chemical plating, wherein the heating temperature is 90 ℃, the addition amount of the graphite substrate is 0.5g/L, and the chemical plating reaction phenomenon is weak.
And 4, step 4: and after the chemical plating reaction is finished, carrying out suction filtration and cleaning on the obtained composite particles, and then placing the composite particles in a vacuum drying box for drying at the drying temperature of 40 ℃ for 6 hours to obtain the nickel-coated graphite composite particles.
The microscopic morphology of the obtained composite particles is shown in fig. 8, and similar to comparative example 2, only a local position on the surface of the graphite matrix is adsorbed with a nickel particle group, which shows that the plating solution formed by matching two complexing agents of sodium potassium tartrate and ammonium chloride in the comparative example does not have the capability of forming a compact nickel shell layer on the surface of graphite.
Claims (8)
1. A method for preparing nickel-coated graphite composite particles is characterized by comprising the following steps:
step 1: placing the flaky graphite matrix in a sodium hydroxide solution for heating and stirring, completing oil removal cleaning pretreatment, and then performing vacuum drying for later use; wherein the particle size of the flaky graphite matrix is 40-200 μm, the concentration of the sodium hydroxide solution is 75-120 g/L, the stirring and heating temperature is 50-70 ℃, and the stirring time is 20-60 min;
step 2: preparing a chemical nickel plating solution, and adjusting the pH value of the nickel plating solution to 11-13 by using a sodium hydroxide solution; the nickel plating solution comprises nickel sulfate, sodium potassium tartrate, sodium citrate and hydrazine hydrate;
and step 3: under the condition of heating and stirring, placing the graphite matrix to be used in the step 1 into the nickel plating solution prepared in the step 2 for chemical plating; wherein the heating temperature is 75-90 ℃, and the chemical plating time is 40-90 min;
and 4, step 4: and after the chemical plating reaction is finished, carrying out suction filtration, cleaning and vacuum drying on the obtained composite particles to obtain the nickel-coated graphite composite particles.
2. The preparation method according to claim 1, wherein in the step 2, the mass concentrations of the components in the nickel plating solution are respectively as follows: 16-47 g/L of nickel sulfate, 9.4-24 g/L of sodium potassium tartrate, 23.5-96 g/L of sodium citrate and 10-25 ml/L of 80 wt.% hydrazine hydrate.
3. The preparation method according to claim 1 or 2, wherein in the step 2, the mass ratio of the potassium sodium tartrate to the sodium citrate is 1: 2.5-4.
4. The preparation method according to claim 1 or 2, wherein in the step 3, the addition amount of the graphite matrix is 0.5-5 g/L.
5. The method according to claim 4, wherein the graphite matrix is added in an amount of 0.5g/L in the step 3.
6. The preparation method according to claim 1, 2 or 5, wherein in the step 1, the temperature of vacuum drying is 30-80 ℃, and the drying time is 12-24 h; in the step 4, the temperature of vacuum drying is 30-50 ℃, and the drying time is 5-8 h.
7. A nickel-coated graphite composite particle obtained by the production method according to any one of claims 1 to 6.
8. The application of the nickel-coated graphite composite particles obtained by the preparation method according to any one of claims 1 to 6 in the field of electromagnetic wave shielding is characterized in that the nickel-coated graphite composite particles are mixed with organic silicone oil to prepare a conductive shielding silicone rubber sheet with the thickness of 0.5-2 mm, and the electromagnetic wave shielding performance of the conductive shielding silicone rubber sheet in the 5.85-26.5 GHz band is tested by a waveguide method.
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Application publication date: 20220705 |