CN118077021A - Conductive carbon particles having excellent corrosion resistance - Google Patents
Conductive carbon particles having excellent corrosion resistance Download PDFInfo
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- CN118077021A CN118077021A CN202180103115.1A CN202180103115A CN118077021A CN 118077021 A CN118077021 A CN 118077021A CN 202180103115 A CN202180103115 A CN 202180103115A CN 118077021 A CN118077021 A CN 118077021A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000002245 particle Substances 0.000 title claims abstract description 132
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 114
- 238000005260 corrosion Methods 0.000 title abstract description 16
- 230000007797 corrosion Effects 0.000 title abstract description 16
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 121
- 229910052709 silver Inorganic materials 0.000 claims abstract description 68
- 239000004332 silver Substances 0.000 claims abstract description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 61
- 239000010949 copper Substances 0.000 claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 67
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000007772 electroless plating Methods 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 44
- 239000002184 metal Substances 0.000 abstract description 44
- 239000010410 layer Substances 0.000 description 140
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011247 coating layer Substances 0.000 description 13
- 229910052763 palladium Inorganic materials 0.000 description 13
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XDIYNQZUNSSENW-UUBOPVPUSA-N (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O XDIYNQZUNSSENW-UUBOPVPUSA-N 0.000 description 1
- STGNLGBPLOVYMA-TZKOHIRVSA-N (z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-TZKOHIRVSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SDVHRXOTTYYKRY-UHFFFAOYSA-J tetrasodium;dioxido-oxo-phosphonato-$l^{5}-phosphane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)P([O-])([O-])=O SDVHRXOTTYYKRY-UHFFFAOYSA-J 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Non-Insulated Conductors (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The purpose of the present invention is to provide conductive carbon particles having a metal layer formed on the surface thereof, which metal layer has excellent conductivity, corrosion resistance and adhesion to carbon particles. In order to achieve the above object, the present invention provides conductive carbon-based particles comprising: a first layer formed on the surface of the carbon particles and containing silver oxide; a second layer formed on the first layer and containing copper; and a third layer formed on the second layer and containing nickel or silver.
Description
Technical Field
The present invention relates to conductive carbon particles having a conductive metal coating layer, and more particularly, to conductive carbon particles having a multilayer structure excellent in corrosion resistance, and a method for manufacturing the same, in which a copper metal layer is formed on a surface without an expensive palladium catalyst layer and a nickel coating layer or a silver coating layer is additionally formed to protect the copper metal layer, thereby realizing the multilayer structure and excellent corrosion resistance.
Background
Conductive particles are very widely used in electronic materials. Among them, metal particles such as copper and nickel have high conductivity and high price competitiveness, and thus are used in various ways for films, adhesives, coating slurries, and the like of many electronic components, which require conductivity.
However, it is difficult to prepare particles of various sizes during the synthesis process, and to maintain uniformity of particle size and spherical shape among particles, and thus it is difficult to prepare a film or adhesive layer of uniform thickness and to maintain uniformity of contact characteristics when preparing a conductive film or adhesive. In order to compensate for the poor contact characteristics, a large amount of metal particles are added to the film or the adhesive, and a high volume ratio of the metal particles may cause problems such as the film or the adhesive layer becoming heavy and the adhesive force being poor.
On the other hand, carbon-based particles having a low density, excellent chemical resistance, and conductivity equal to or higher than a predetermined value are also often used as the conductive material, and examples of the carbon-based particles include graphite particles, graphene particles, and Carbon Nanotube (CNT) particles. However, films or adhesive layers made of such carbon-based particles still have a problem of lower conductivity than metal particles.
In order to overcome such problems, it is necessary to use conductive carbon particles in which a conductive metal layer such as copper, nickel, silver, or gold is formed on the surface of carbon particles such as graphite, graphene, or carbon nanotubes, which have low density and excellent chemical resistance.
However, the carbon-based particles and the metal layer as the base material are heterogeneous materials of different types, and there is a problem in that it is difficult to maintain the binding force. In order to form a metal coating layer on the surface of a heterogeneous material such as a carbon-based material or ceramic, a method of forming a metal layer after forming a catalytic layer using palladium is generally used in many cases, but palladium is too expensive, and thus there is a problem in that the process cost increases.
On the other hand, the metal layer coated on the surface of the carbon-based particles may be composed of various metals, and although copper has excellent conductivity close to silver, there is a problem that it is easily oxidized, nickel has advantages in terms of long-term reliability and the like due to excellent corrosion resistance, but has a problem of low conductivity. Silver (Ag) as another metal is excellent in conductivity and corrosion resistance, but has a problem of excessive price.
As described above, the metal layer formed on the surface of the carbon-based particles has a problem that it is difficult to satisfy all of the required quality.
Disclosure of Invention
Technical problem
An object of the present invention is to provide conductive carbon particles having a metal layer formed on the surface thereof, the metal layer having excellent conductivity, corrosion resistance and adhesion to the carbon particles.
It is still another object of the present invention to provide a method for producing conductive carbon particles, which can form a metal layer having excellent conductivity, corrosion resistance, and adhesion to carbon particles on the surface of the conductive carbon particles at low cost.
Technical proposal
In order to achieve the above object, the present invention may provide a conductive carbon-based particle comprising: a first layer formed on the surface of the carbon particles and containing silver oxide; a second layer formed on the first layer and containing copper; and a third layer formed on the second layer and containing nickel or silver.
The carbon-based particles are one or more selected from the group consisting of graphite, graphene, and carbon nanotubes.
The first layer further contains metallic silver, and the molar ratio of the silver element in the silver oxide to the silver element in the metallic silver (Agx+/Ag 0 (0 < x.ltoreq.3)) is in the range of 1 to 20.
And, the first layer may further include tin.
The silver content of the first layer may be 10 to 1000ppm based on the total weight of the conductive carbon particles.
Further, the third layer may contain phosphorus in addition to the nickel.
And, the third layer may contain 0.1 to 13.0 weight percent of phosphorus.
The preparation method of the conductive carbon particles of the invention can comprise the following steps: (a) Hydrophilizing the surface of the carbon particles; (b) A first layer forming step of coating silver oxide on the carbon-based particles hydrophilized on the surface; (c) A second layer forming step of plating copper on the first layer by electroless plating; and (d) a third layer forming step of plating nickel or silver on the second layer by electroless plating.
And, a step of forming a tin layer may be further included between the steps (a) and (b).
Further, the method may further include a post-treatment step after the step (b) and before the step (c), wherein the amount of the silver oxide is adjusted by stirring the carbon-based particles having the first layer formed therein in an aqueous solution having a pH of 8 to 14 and a temperature of 20 to 80 ℃.
ADVANTAGEOUS EFFECTS OF INVENTION
The conductive carbon particles of the present invention are suitable for various electronic components that require conductivity because of low cost, excellent conductivity, and excellent corrosion resistance, and can achieve weight reduction of the component and improvement of conductivity and reliability because of excellent binding force of the surface metal layer.
In addition, the conductive carbon particles having excellent conductivity and reliability can be mass-produced by a low-cost process by the method for producing conductive carbon particles provided by the present invention.
Drawings
Fig. 1 is a scanning electron microscope image of conductive carbon-based particles according to examples and comparative examples of the present invention.
FIG. 2 shows the result of X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy, XPS) analysis of conductive carbon particles according to one embodiment of the present invention.
Detailed Description
The structure and function of the embodiments of the present invention are described below with reference to the drawings. In the following description of the present invention, a detailed description of the related known functions or configurations will be omitted when it is determined that the gist of the present invention may be unnecessarily obscured. When a certain component is indicated as "including" a certain component, unless otherwise specified, it is meant that other components may be included, rather than excluded.
Carbon particles have the advantages of excellent chemical resistance and low density, but have a limitation in use as conductive particles because of low conductivity. In order to overcome this, when a conductive metal layer is formed on the surface, conductivity can be imparted to carbon-based particles of various shapes and sizes.
However, since carbon and metal are heterogeneous materials, the adhesion is very low, and it is difficult to form a metal layer on the surface of carbon particles. In order to overcome this problem, conventionally, a method of forming an interlayer capable of bonding to a site between a metal layer imparting conductivity and carbon-based particles has been used, and a catalyst layer containing palladium has been formed as such an interlayer. Such palladium catalytic layer guides the formation of copper, nickel, silver, etc. as a metal layer along the site. However, palladium is known to be a noble metal having a high valence and is more expensive than gold recently, and thus there is a problem that the preparation using it only results in excessive process costs.
In order to solve such a problem, the inventors of the present invention studied an intermediate layer which is less expensive than palladium and can sufficiently provide a binding force with the surface of carbon-based particles. As is well known, silver oxide is excellent in bonding force with a metal and can be bonded to the surface of carbon particles in a field as an oxide, and a technique of forming a metal coating layer by preparing the silver oxide as an intermediate layer has been developed.
Finally, in the case where the intermediate layer is formed by silver oxide alone or the intermediate layer is formed by compositing silver oxide and metallic silver, the metallic layer formed as a later can be firmly bonded to the carbon-based particles, which is the same effect as the case of using the existing palladium-containing layer or can exhibit a better bonding force.
On the other hand, the characteristics of the conductive carbon particles will be determined according to the type of the metal layer formed on the surface of the carbon particles, and copper has excellent conductivity but is liable to be oxidized, which causes a problem in terms of reliability. In contrast, nickel has a problem of inferior conductivity to copper, although it has excellent corrosion resistance. Silver has excellent corrosion resistance and conductivity, but has a problem of high price. As described above, there is a problem that it is difficult to satisfy all the characteristics required in industrial production.
In order to solve such a problem, the inventors of the present invention have invented conductive carbon-based particles having a metal layer of a multilayer structure formed on the surface thereof by forming a copper metal layer first by forming the metal layer into a multilayer structure and forming a nickel or silver metal layer on the copper metal layer in order to protect the copper metal layer.
Accordingly, the present invention may provide conductive carbon-based particles including: a first layer formed on the surface of the carbon particles and containing silver oxide; a second layer formed on the first layer and containing copper; and a third layer formed on the second layer and containing nickel or silver.
The carbon-based particles constituting the core of the conductive carbon-based particles may be one or more selected from the group consisting of graphite, graphene, and carbon nanotubes.
Conductive carbon particles have low density and excellent chemical resistance, and can have various particle sizes, and thus are advantageously used in various electronic parts. For this reason, it is preferable to select graphite, graphene or carbon nanotubes as carbon particles constituting the core, and all of these are commercialized as products having various characteristics, so that various conductive carbon particles can be produced by using them. In particular, graphite has been commercialized in various particle sizes and shapes according to the kinds of artificial graphite, natural graphite, and the like, and various products have been achieved due to various choices in characteristics and unit price.
As described above, the surface of the carbon-based particles is difficult to bond to the metal layer due to the characteristics of the material. In order to modify such surface characteristics, it is necessary to form a catalytic layer, but in the present invention, a first layer is formed as a catalytic layer containing silver oxide instead of the conventional catalytic layer containing palladium. Since silver oxide bonds well to carbon and also to metal, the carbon particles constituting the core can be strongly bonded to the metal layer on the surface.
In the present invention, the first layer containing silver oxide may further contain tin, which is an element for inducing good adhesion of silver oxide to the surface of the carbon-based particles, and if the coating operation is performed in an aqueous solution, hydrophilization of the surface of the carbon-based particles is improved, thereby facilitating adhesion of silver element to the surface of the carbon-based particles. Such tin may constitute the first layer together with silver oxide, or may be formed between the first layer containing silver oxide and the surface of the carbon-based particles.
In the present invention, the first layer including silver oxide may include metallic silver in addition to silver oxide, and if metallic silver is further included, bonding with copper, which is a metal included in the second layer, may be made stronger. The silver oxide makes the bonding with the carbon-based particles stronger, and the bonding between the metallic silver and such silver oxide becomes stronger while providing a strong bonding force with copper, which is also a metal, and finally further enhances the bonding force between the second layer containing copper and the carbon-based particles.
In this case, preferably, the molar ratio of the silver element in the silver oxide to the silver element in the metallic silver (Ag x+/Ag0 (0 < x.ltoreq.3)) in the first layer is in the range of 1 to 20.
As described above, the inclusion of metallic silver makes the bonding between the first layer including silver oxide and the second layer including copper firm, but if the proportion of silver element in metallic silver is higher than that in silver oxide, the bonding force with the surface of the carbon-based particles of the first layer by silver oxide becomes poor, so that it is not preferable. Therefore, the molar ratio of the silver element in the silver oxide to the silver element in the metallic silver is preferably 1 to 20 so that the proportion of the silver element in the silver oxide is higher, more preferably 1 to 10. The molar ratio can be determined by X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy, XPS).
Wherein the oxidation number of silver in the silver oxide may be +1 to +3, and in the amorphous state, the oxidation number may not be positive, and thus the oxidation number of silver in the silver oxide may be more than 0 and not more than 3.
The first layer may further contain palladium, and the bonding between the surface of the carbon-based particle and the silver oxide and the bonding of the second layer may be further enhanced by containing palladium. In this case, palladium may be contained in an amount significantly smaller than that contained in the existing conductive carbon-based particles without silver oxide. For example, the amount of palladium used in the process for producing conductive carbon particles is usually in the range of 100 to 1000ppm based on conventional conductive carbon particles, but the conductive carbon particles of the present invention may be used in the range of more than 0 and not more than 50 ppm.
The silver content of the first layer may be 10 to 1000ppm based on the total weight of the conductive carbon particles.
The metal silver or silver oxide formed in the first layer is not preferable because the metal silver or silver oxide is not less than a predetermined amount, and the second layer is not more bonded to the metal silver or silver oxide. More preferably 10 to 500ppm.
In the present invention, the first layer may be formed in a discontinuous island shape on the surface of the carbon-based particle. The first layer is a layer that provides the second layer that imparts conductivity with a binding force to the carbon-based particles, and can provide the second layer with a sufficient binding force even in the form of discontinuous islands.
On the other hand, the first layer may be formed in a continuous film shape, and in this case, the first layer may occupy at least 50% or more of the surface area of the carbon-based particles. This is because, in the case of forming a continuous film, a sufficient binding force can be provided to the second layer only by at least 50% or more of the surface area of the particles.
A second layer containing copper as a metal excellent in conductivity will be formed on the first layer containing silver oxide. Copper has excellent conductivity among metals, and thus, conductive carbon particles have excellent conductivity.
Such a second layer containing copper may account for 5 to 40 weight percent of the total conductive carbon particles, but if it is less than 5 weight percent, the conductivity may be deteriorated, and if it is more than 40 weight percent, the density of the entire conductive carbon particles will become high, and the risk of falling off of the second layer will increase, so that it is not preferable. Therefore, the content of the second layer in the conductive carbon-based particles is preferably 5 to 30 weight percent, more preferably 8 to 20 weight percent.
On the other hand, in the present invention, the content of copper in the second layer containing copper is 90 weight percent or more, because if it is less than 90 weight percent, the conductivity of the second layer will be deteriorated.
In the present invention, a third layer including nickel or silver may be reformed over the second layer including copper.
Such a third layer containing nickel or silver will have excellent conductivity while preventing oxidation of metallic copper formed on the second layer, and eventually can enable conductive carbon-based particles to secure both conductivity and reliability.
When a metal layer containing nickel having excellent corrosion resistance is formed as the third layer, nickel as a metal is formed while protecting the second layer, and thus conductivity of a predetermined level or higher can be ensured.
Such a third layer contains not only nickel but also phosphorus, and although the inclusion of phosphorus slightly decreases conductivity, the third layer preferably contains nickel and phosphorus in the case of a product in which reliability is important because chemical resistance and oxidation resistance are improved. In the case of containing phosphorus, the content of phosphorus in the third layer is preferably 0.1 to 13.0 weight percent, and if it is too low, the desired improvement in chemical resistance and oxidation resistance cannot be achieved, and if it is more than 13 weight percent, sufficient conductivity cannot be obtained. More preferably, the phosphorus content is 0.5 to 6 weight percent.
On the other hand, the third layer may contain metallic silver instead of nickel, and silver has a disadvantage of being expensive although it is very desirable in terms of characteristics as a metal excellent in both corrosion resistance and electrical conductivity. Therefore, in terms of conductivity, if silver having excellent conductivity, which protects copper, is formed as the third layer on the second layer made of copper having the same level as silver, the reliability can be ensured while minimizing the amount of expensive silver used, and the conductivity of the conductive carbon-based particles can be maximized.
In addition, the present invention provides a method for preparing conductive carbon-based particles, comprising: (a) Hydrophilizing the surface of the carbon particles; (b) A first layer forming step of coating silver oxide on the carbon-based particles hydrophilized on the surface; (c) A second layer forming step of plating copper on the first layer by electroless plating; and (d) a third layer forming step of plating nickel or silver on the second layer by electroless plating.
In order to produce conductive carbon particles, a hydrophilization step of hydrophilizing the surface of the carbon particles by introducing a chemical functional group is first required. This hydrophilization step can be carried out in a strongly acidic aqueous solution having a pH of 3 or less. This is because the chemical functional group can be attached to the surface of the carbon-based particle in the field by breaking part of the carbon bonds on the surface of the carbon-based particle by the strong acid solution. Therefore, in order to treat the surface of the stable carbon-based particles, a strong acid atmosphere of an inorganic acid such as sulfuric acid, nitric acid, or hydrochloric acid having a pH of 3 or less is preferably formed.
On the other hand, as described above, the hydrophilization treatment of the carbon-based particles may be performed in a strongly acidic aqueous solution, but dry hydrophilization may be performed by modifying the surfaces of the carbon-based particles by plasma treatment.
After the hydrophilization treatment, a first layer comprising silver oxide will be formed, which may be coated with silver oxide and tin together. Tin can improve the binding force of silver oxide on the surface of hydrophilized carbon particles.
In order to control the surface of the hydrophilized carbon particles more precisely, a tin layer may be formed on the surface of the hydrophilized carbon particles, and then a first layer containing silver oxide may be formed.
The formation of the first layer comprising silver oxide may be achieved in an alkaline aqueous solution having a pH of 8 or more. This is because silver oxide will form well in an alkaline atmosphere at a pH of 8 or more. More preferably, this is accomplished in an aqueous solution having a pH in the range of 9 to 11.
In the method for producing conductive carbon particles, after the step (b) and before the step (c), a post-treatment step of stirring the carbon particles having the first layer formed therein in an aqueous solution having a pH of 8 to 14 and a temperature of 20 to 80 ℃ may be further included to adjust the amount of silver oxide.
When the first layer is formed in the aqueous solution, silver ions in the aqueous solution are reduced to adhere to the surfaces of the carbon-based particles in the form of metallic silver other than silver oxide. If the ratio of such metallic silver is too high, there is a possibility that the bonding force with the carbon-based particles and the first layer will be poor, which is not preferable. Thus, in order to increase the content of silver oxide to a desired level, the amount of silver oxide can be adjusted by treatment in an alkaline aqueous solution at an appropriate temperature.
By forming the second layer containing copper having conductivity after adjusting the amount of silver oxide in this manner, conductive carbon-based particles having excellent binding force with the metal coating layer and the carbon-based particles that impart conductivity can be provided.
Best mode for carrying out the invention
Hereinafter, in order to fully understand the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings.
The embodiments of the present invention will be described more fully with reference to those skilled in the art, and the following embodiments may be modified to various other embodiments, and the scope of the present invention is not limited to the following embodiments. Rather, these embodiments will be so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.
Example 1
To 100g of deionized water was added 3g of hydrochloric acid (35% solution) and the temperature was raised to 60 ℃. Thereafter, 10g of graphite having a D 50 of 20 μm was put in and stirred for 10 hours, thereby hydrophilizing the surface of the graphite powder. Thereafter, the hydrophilized graphite powder was recovered, and after stirring and washing in 100g of deionized water again for 3 times, it was recovered.
The recovered graphite particles were put into an aqueous solution of 1.5g of stannous chloride dihydrate (SnCl 2·2H2 O) and 6ml of hydrochloric acid (35% solution) dissolved in 100g of deionized water and stirred for 30 minutes, thereby forming a tin layer. The temperature of the aqueous solution was maintained at 35 ℃.
After graphite particles having a tin layer formed thereon were collected by filtration, a silver nitrate solution in which 0.15g of silver nitrate (AgNO 3) was dissolved in 100g of deionized water was added thereto and stirred. In this case, 28% ammonia was titrated to adjust the pH to 9.3.
The temperature was maintained at 40 ℃ and stirring was performed for 1 hour to form a silver oxide layer. The recovery was performed by filtration after 1 hour, followed by stirring in 200g of deionized water and washing 3 times. A part of the powder on which the silver oxide layer was formed was collected to conduct surface analysis based on X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy, XPS).
The powder having the silver oxide layer formed thereon was recovered, and a copper coating layer was formed by electroless plating. An aqueous solution of copper sulfate complex was prepared by adding 40g of ethylenediamine tetraacetic acid (EDTA, ethylene-diamine-TETRAACETIC ACID) as a complex, 30g of NaOH, and 20g of copper sulfate to 300g of deionized water solution, placing graphite powder formed with a silver oxide layer and stirring, and titrating a formaldehyde (formaldehyde) solution as a reducing agent to form a copper-containing coating.
A nickel coating layer was reformed on the graphite powder on which the copper coating layer was formed, and for this purpose, a nickel coating solution composed of 20g of nickel chloride hexahydrate (NiCl 2·6H2 O), 10g of sodium acetate, 5g of maleic acid (MALEIC ACID), 30g of sodium hypophosphite (sodium hypophosphate) as a reducing agent, and 3ml of lead acetate (LEAD ACETATE) was put into the powder on which the copper coating layer was formed, stirred, and maintained at a temperature of 70 to 90℃for 2 hours was subjected to electroless plating.
Example 2
The process was carried out in the same manner as in example 1 until a copper coating layer was formed, after which a coating layer containing silver was formed by electroless plating. For this, after preparing a silver coating solution by adding 2g of ethylenediamine tetraacetic acid (EDTA, ethylene-diamine-TETRAACETIC ACID), 2.5ml of 28% ammonia water, 3g of silver nitrate (AgNO 3) to 300g of deionized water, graphite particles having a copper coating formed thereon were placed therein and stirred, and a reducing solution of 10g of glucose (glucose) and 2g of sodium hydroxide dissolved in 50g of deionized water was titrated for one hour to form a third layer containing silver.
Example 3
After the first layer containing silver oxide was formed on the surface of the graphite particles in the same manner as in example 1, a post-treatment was performed in an alkaline aqueous solution. For the post-treatment, 100g of deionized water was put into 28% ammonia water, and after maintaining the temperature at 60 ℃, graphite particles having a first layer formed therein were put into the solution and stirred. The pH of the aqueous solution was 10.1 prior to placement of the graphite particles.
Thereafter, a second layer containing copper and a third layer containing nickel were formed in the same manner as in example 1.
Comparative example 1
Hydrophilization treatment was performed in the same manner as in example 1 and a tin layer was formed. After that, a silver oxide layer is not formed, but electroless plating is directly performed to sequentially form a second layer including copper and a third layer including nickel. Electroless plating of copper and nickel was performed in the same manner as in example 1.
Comparative example 2
A first layer containing silver oxide was formed on the surface of the graphite particles in the same manner as in example 1. Thereafter, vitamin C (Ascorbic acid) is put into the aqueous solution to bring a part of silver oxide on the surface into a metallic silver state, and then a second layer containing copper and a third layer containing nickel are sequentially formed by performing electroless plating. Electroless plating of copper and nickel was performed in the same manner as in example 1.
Comparative example 3
The process was performed in the same manner as in example 1 until the copper coating was formed, and the subsequent steps were not performed.
After the conductive carbon-based particles thus prepared were formed into the first layer, analysis of the silver element ratio of silver oxide and metallic silver, analysis of the silver element content, nickel content, phosphorus content, and observation of the coating state based on a scanning electron microscope (Scanning Electron Microscope, SEM) were performed. The elemental silver ratio was analyzed by taking a sample after formation of the first layer and by X-ray photoelectron spectroscopy (XPS). The elemental silver content, nickel content, and phosphorus content were analyzed by inductively coupled plasma mass spectrometry (Inductively Coupled PLASMA MASS Spectrometer, ICP).
Reliability was evaluated by a reflow test in which a polyimide film was coated with conductive carbon particles prepared in examples 1 to 3 and comparative examples 1 and 2 and an acrylic binder by mixing predetermined amounts, and after drying, the polyimide film was maintained on molten lead for 30 seconds, and then conductivity was measured.
The results are shown in table 1. Wherein the content of Cu shows the weight percentage of copper element in the total conductive graphite particles.
TABLE 1
| Agx+/Ag0 | Cu content (wt%) | Coating state | Corrosion resistance (mΩ) | |
| Example 1 | 1.91 | 10.5 | Good quality | 35 |
| Example 2 | 2.51 | 12.1 | Good quality | 19 |
| Example 3 | 7.83 | 9.8 | Good quality | 45 |
| Comparative example 1 | - | - | Failure to apply | - |
| Comparative example 2 | 0.51 | Failure of | 120 | |
| Comparative example 3 | 1.85 | 11 | Good quality | Not measured |
Fig. 1 shows a scanning electron micrograph of conductive graphite particles of an embodiment. Part (a) in fig. 1 is a scanning electron microscope image of the sample in example 1, part (b) in fig. 1 is a scanning electron microscope image of the sample in example 2, part (c) in fig. 1 is a scanning electron microscope image of the sample in comparative example 1, and part (d) in fig. 1 is a scanning electron microscope image of the sample in comparative example 2.
The samples of example 1 and example 2 each showed that a dense coating was formed, but in comparative example 1 in which the first layer containing silver oxide was not formed well, and in comparative example 2 in which the content of metallic silver in the first layer was high, it was found that the coating was not dense and the bonding property was not strong.
Fig. 2 is a result of measuring a silver element ratio of silver oxide and metallic silver of the first layer in the sample in example 3. As a result of the X-ray photoelectron spectroscopy technique, the silver proportion in the reduced state and the silver proportion in the oxidized state can be determined by the peak ratio. In example 3, their molar ratio (Ag x+/Ag0) was 7.83.
On the other hand, as shown in table 1, the corrosion resistance was evaluated by the reflow test, and in examples 1 to 3, the resistance of the film using the conductive graphite particles after the reflow test was 50mΩ or less, which is good, whereas in comparative example 2 in which the formation of the coating layer was unstable, the resistance was significantly increased, and in the sample of comparative example 3 in which the third layer as the protective layer was not formed, the resistance was too high to be measured.
Claims (10)
1. A conductive carbon-based particle, comprising:
a first layer formed on the surface of the carbon particles and containing silver oxide;
a second layer formed on the first layer and containing copper; and
And a third layer formed on the second layer and containing nickel or silver.
2. The conductive carbon particle according to claim 1, wherein the carbon particle is one or more selected from the group consisting of graphite, graphene, and carbon nanotube.
3. The conductive carbon particle according to claim 1, wherein the first layer further comprises metallic silver, and a molar ratio of the silver element in the silver oxide to the silver element in the metallic silver is in a range of 1 to 20, that is, ag x+/Ag0 is in a range of 1 to 20, wherein 0< x.ltoreq.3.
4. The conductive carbon particle of claim 1, wherein said first layer further comprises tin.
5. The conductive carbon particle according to claim 1, wherein the silver content of the first layer is 10 to 1000ppm based on the total weight of the conductive carbon particle.
6. The conductive carbon particle of claim 1, wherein said third layer further comprises phosphorus in addition to said nickel.
7. The conductive carbon particle as recited in claim 6, wherein said third layer contains 0.1 to 13.0 weight percent phosphorus.
8. A method for preparing conductive carbon particles, comprising:
(a) Hydrophilizing the surface of the carbon particles;
(b) A first layer forming step of coating silver oxide on the carbon-based particles hydrophilized on the surface;
(c) A second layer forming step of plating copper on the first layer by electroless plating; and
(D) And a third layer forming step of plating nickel or silver on the second layer by electroless plating.
9. The method of producing conductive carbon particles according to claim 8, further comprising a step of forming a tin layer between the step (a) and the step (b).
10. The method according to claim 8, further comprising a post-treatment step of stirring the carbon particles having the first layer formed therein in an aqueous solution having a pH of 8 to 14 and a temperature of 20 to 80 ℃ after the step (b) and before the step (c), thereby adjusting the amount of the silver oxide.
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| PCT/KR2021/013907 WO2023058797A1 (en) | 2021-10-08 | 2021-10-08 | Conductive carbon-based particles having excellent corrosion resistance |
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| JP5375343B2 (en) * | 2009-06-04 | 2013-12-25 | 日立金属株式会社 | Bonding material, manufacturing method thereof, and mounting method using the same |
| WO2014182141A1 (en) * | 2013-05-10 | 2014-11-13 | 주식회사 엘지화학 | Copper containing particle and method for manufacturing same |
| KR101543971B1 (en) * | 2014-10-07 | 2015-08-12 | 성균관대학교산학협력단 | Method for preparing metal oxide nanoparticles/graphene composite using supercritical fluides and metal oxide nanoparticles/graphene composite prepared thereby |
| KR102150161B1 (en) * | 2018-09-27 | 2020-08-31 | 주식회사 씨앤씨머티리얼즈 | Nickel-coated super-abrasive particles with excellent magnetic properties and wire saw using the same |
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