CN114628058B - Copper terminal electrode slurry for multilayer chip ceramic capacitor and preparation method thereof - Google Patents
Copper terminal electrode slurry for multilayer chip ceramic capacitor and preparation method thereof Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 267
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 97
- 239000010949 copper Substances 0.000 title claims abstract description 97
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 48
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 41
- 239000011521 glass Substances 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 34
- 239000002003 electrode paste Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 239000000084 colloidal system Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000005096 rolling process Methods 0.000 claims description 14
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940116411 terpineol Drugs 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000000280 densification Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- 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
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
- H01G4/0085—Fried electrodes
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- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Spectroscopy & Molecular Physics (AREA)
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- Ceramic Capacitors (AREA)
Abstract
The invention discloses copper terminal electrode slurry for a multilayer chip ceramic capacitor and a preparation method thereof. The copper terminal electrode slurry for the multilayer chip ceramic capacitor comprises nano Ag coated plate-shaped copper powder, glass powder, resin and an organic solvent. The copper end electrode slurry prepared by the invention has high compactness and low sintering temperature, meets the requirements of the copper end electrode slurry for the small-size and high-capacity multilayer chip ceramic capacitor, has simple process and low production cost, and can realize industrial production.
Description
Technical Field
The invention belongs to the field of terminal electrodes for multilayer chip ceramic capacitors, and particularly relates to copper terminal electrode slurry for a small-size and high-capacity multilayer chip ceramic capacitor and a preparation method thereof.
Background
One of the main application fields of the copper end electrode paste is a multilayer chip Ceramic capacitor (MLCC), the copper end electrode paste of the multilayer Ceramic capacitor is mainly applied to a Ceramic formed by laminating, cutting and co-firing MLCC nickel paste and a dielectric film tape, the copper end electrode paste is wrapped at two ends of the MLCC Ceramic by a copper bonding machine, glue discharging and sintering are carried out by a nitrogen atmosphere chain sintering furnace, and a complete MLCC is prepared by an electroplated nickel Layer and an electroplated tin Layer at the later stage.
At present, the sintering temperature of the traditional copper end electrode slurry is 800-850 ℃, and the compactness of the traditional copper end electrode slurry is improved by adopting ball-sheet mixed copper powder (the mass ratio of ball powder to sheet powder is 2: 8-9: 2). With the rapid development of modern intelligent devices, the highly integrated design of circuit boards puts requirements on small size and high capacity on MLCCs. In the MLCC design stage, BaTiO with the thickness of 150nm or less is selected as the dielectric film layer 3 The formula powder meets the requirements of small size and high capacity. TiO 2-BaTiO 3 The particle size of the base medium material powder is reduced, and BaTiO is subjected to copper end slurry sintering under low oxygen partial pressure in a nitrogen atmosphere at 800-850 DEG C 3 The dielectric material is easily reduced to a semiconductor. Meanwhile, the small-size high-capacity MLCC puts a thinner requirement on the thickness of the sintered copper end electrode, and the electrode with poor compactness is easy to cause the permeation of electroplating solution in the subsequent electroplating operation of the MLCC, and both of the electroplating solution and the electroplating solution can cause the instability of the electrical performance of the MLCC finished product.
Therefore, there is a need in the art for a copper termination electrode paste for small-sized high-capacity MLCCs and a method for preparing the same.
Disclosure of Invention
The invention aims to provide copper end electrode slurry for a small-size high-capacity MLCC and a preparation method thereof. The copper-end electrode slurry disclosed by the invention is low in sintering temperature (700-750 ℃), high in compactness, simple in preparation process and low in cost, meets the requirements of small-size high-capacity MLCC, and can realize industrial production.
Specifically, the invention provides copper end electrode slurry for a multilayer chip ceramic capacitor, which comprises the following components in a mass ratio of 100: (8-16): (6-12): (25-40) coating the plate-shaped copper powder with the nano Ag, the glass powder, the resin and the organic solvent, wherein the thickness of the plate-shaped copper powder coated with the nano Ag is 0.3-1.5 mu m.
In one or more embodiments, the ratio of the thickness of the nano-Ag coated platy copper powder to the minor axis diameter is between 5% and 80%.
In one or more embodiments, the ratio of the thickness of the nano-Ag coated platy copper powder to the minor axis diameter is between 20% and 60%.
In one or more embodiments, the raw materials of the glass frit include the following components in weight percent: b is 2 O 3 32-35％，SiO 2 21-28％，ZnO 20-22％，Al 2 O 3 16-18％，NbO 3-5％。
In one or more embodiments, the glass frit has an average particle size of 1 to 2.5 μm.
In one or more embodiments, the resin is an acrylic resin.
In one or more embodiments, the organic solvent is selected from one or more of octanol, terpineol, and hydrogenated terpineol.
In one or more embodiments, the nano Ag-coated plate-like copper powder, the glass powder, the resin, and the organic solvent are in a mass ratio of 100: (10-14): (7.5-10.5): (26-36).
In one or more embodiments, the nano-Ag coated platy copper powder is produced using a method comprising:
(1) uniformly mixing spherical copper powder, nano Ag colloid, binder and dispersant to obtain nano Ag/spherical copper powder slurry;
(2) and stirring and grinding the nano Ag/spherical copper powder slurry by using a grinder, and then performing baking treatment and inert gas atmosphere heat treatment to obtain the nano Ag coated platy copper powder.
In one or more embodiments, in step (1), the spherical copper powder has an average particle size of 0.5 to 2.5 μm.
In one or more embodiments, in the step (1), the mass concentration of the nano-Ag in the nano-Ag colloid is 5000-10000ppm, and the particle size of the nano-Ag is 10-30 nm.
In one or more embodiments, in step (1), the binder comprises a resin and an organic solvent.
In one or more embodiments, in step (1), the dispersant is ethanol.
In one or more embodiments, in the step (1), the mass ratio of the spherical copper powder, the nano Ag colloid, the binder and the dispersant is 100: (8-12): (3-10): (70-80).
In one or more embodiments, in step (1), the linear velocity of the mixing is from 40 to 60m/s and the mixing time is from 0.5 to 1.5 h.
In one or more embodiments, in the step (2), the rotating speed of the blender is 60-80rpm/min, and the stirring time is 0.5-1.5 h.
In one or more embodiments, in the step (2), the mill uses zirconia beads having a diameter of 0.28 to 0.32mm as a grinding medium.
In one or more embodiments, in step (2), adding grinding media to the blender in an amount of 30-40% by volume of the blender.
In one or more embodiments, in step (2), the baking temperature is 80-100 ℃ and the baking time is 4-6 h.
In one or more embodiments, in the step (2), the temperature of the inert gas atmosphere heat treatment is 150-.
In one or more embodiments, in step (2), the inert gas is nitrogen.
In one or more embodiments, the binder is a resin that is acrylic.
In one or more embodiments, the organic solvent in the binder is selected from one or more of octanol, terpineol, and hydrogenated terpineol.
In one or more embodiments, the mass fraction of the resin in the binder is from 35 to 45%.
The present invention also provides a method of preparing a copper terminal electrode paste for a multilayer chip ceramic capacitor according to any one of the embodiments herein, the method comprising: and dispersing the resin in a part of organic solvent to obtain a binder, uniformly mixing the nano Ag coated plate-shaped copper powder, the glass powder, the binder and the rest of organic solvent, and rolling by using a rolling mill until the fineness reaches below 7 mu m to obtain the copper end electrode slurry for the multilayer chip ceramic capacitor.
The present invention also provides a multilayer chip ceramic capacitor including copper terminal electrodes prepared using the copper terminal electrode paste for a multilayer chip ceramic capacitor according to any one of the embodiments herein.
The present invention also provides a nano-Ag coated copper plate, as described in any of the embodiments herein.
The present invention also provides a method of reducing the sintering temperature or increasing the sintering compactness of a copper terminal electrode paste for a multilayer chip ceramic capacitor, the method comprising adding the nano Ag-coated plate-shaped copper powder according to any one of the embodiments herein to the copper terminal electrode paste for a multilayer chip ceramic capacitor.
Drawings
FIG. 1 is a flow chart of the preparation process of the copper-terminated electrode paste for small-size high-capacity MLCC of the invention.
Fig. 2 is an electron microscope (SEM) photograph of the plate-like copper powder coated with nano Ag prepared in example 2.
FIG. 3 is an electron microscope (SEM) photograph of a cross section of the copper end electrode paste prepared in comparative example 1 after sintering at 720 ℃.
Fig. 4 is an electron microscope (SEM) photograph of a cross section of the copper end electrode paste prepared in comparative example 1 after sintering at 720 ℃.
Fig. 5 is an electron microscope (SEM) photograph of an end surface of the copper termination electrode paste prepared in example 2 after sintering at 720 ℃.
Fig. 6 is an electron microscope (SEM) photograph of a cross-section of the copper end electrode paste prepared in example 2 after sintering at 720 ℃.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
The terms "comprising," including, "" containing, "and the like, herein, encompass the meanings of" consisting essentially of … … "and" consisting of … …, "e.g., when" A comprises B and C, "A consists essentially of B and C" and "A consists of B and C" are disclosed herein, and are to be considered as having been disclosed herein.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Herein, unless otherwise specified, the percentage means mass percentage, and the proportion means mass ratio.
As used herein, the percentages of the components of the composition add up to 100%.
Herein, when embodiments or examples are described, it is to be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
In the present invention, the sintering densification temperature is determined by sintering the slurry at different sintering temperatures, observing the states of the surface and the cross section, and determining the temperature at which the sintering densification is performed. The sintering densification means that the glass is melted to fill gaps of the copper powder, and the copper powder is connected with each other to form bridges due to thermal motion. Without sintering densification, the copper powder particles were evident on electron microscope (SEM) photographs. Under the condition of overburning, the glass phase can float on the surface of the copper terminal, and the electroplating performance is influenced.
According to the invention, the spherical copper powder is subjected to platy treatment to obtain the nano Ag-coated platy copper powder, and the copper end electrode slurry which is low in sintering densification temperature and high in compactness after sintering can be prepared by using the nano Ag-coated platy copper powder, so that the requirements of small-size high-capacity MLCC (metal-ceramic capacitor) are met.
The copper end electrode slurry comprises or consists of nano Ag coated plate-shaped copper powder, glass powder, resin and an organic solvent.
Nano Ag coated plate-shaped copper powder
In the present invention, the plate-like copper powder coated with nano Ag is formed by subjecting spherical copper powder to plate-like treatment. The thickness range of the nano Ag coated plate-shaped copper powder applicable to the invention is 0.3-1.5 mu m. The thickness range of the plate-shaped copper powder coated with the nano Ag is controlled within the range, so that the electrical property can be ensured while high sintering compactness is obtained.
The ratio of the diameter to the thickness of spherical copper powder is 1:1 theoretically, but in actual production, spherical copper powder is usually not a perfect sphere but a spheroid with a certain deviation between the diameter and the thickness. It is understood that the diameter refers to the radial length of the equatorial plane perpendicular to the thickness direction. When the equatorial plane is elliptical, the diameter of the equatorial plane has the shortest minor axis and the longest major axis. In the present invention, spherical copper powder means copper powder having a ratio of powder thickness to short axis diameter thereof higher than 80%, and flake copper powder means copper powder having a ratio of powder thickness to short axis diameter thereof lower than 5%. The nano Ag coated plate-shaped copper powder is characterized in that the ratio of the thickness to the minor axis diameter is between 5% and 80%, such as 10%, 20%, 30%, 40%, 50%, 60%, 70%, and preferably between 20% and 60%. The invention discovers that the nano Ag coated plate-shaped copper powder with the ratio of the thickness to the minor axis diameter in the range can improve the sintering compactness of the copper end electrode slurry and reduce the sintering temperature.
Therefore, the invention comprises a method for preparing the copper terminal electrode slurry for the multilayer chip ceramic capacitor, a method for reducing the sintering temperature of the copper terminal electrode slurry for the multilayer chip ceramic capacitor or improving the sintering compactness of the copper terminal electrode slurry for the multilayer chip ceramic capacitor, and application of the nano Ag-coated plate-shaped copper powder in preparing the copper terminal electrode slurry for the multilayer chip ceramic capacitor. The method and application include adding the nano-Ag coated plate-shaped copper powder to copper end electrode slurry for a multilayer chip ceramic capacitor in a manner of partially or completely replacing the copper powder.
The nano Ag-coated plate-shaped copper powder can be prepared by adopting a method comprising the following steps of:
(1) uniformly mixing spherical copper powder, nano Ag colloid, binder and dispersant to obtain nano Ag/spherical copper powder slurry;
(2) and stirring and grinding the nano Ag/spherical copper powder slurry by using a grinder, and then performing baking treatment and inert gas atmosphere heat treatment to obtain the nano Ag coated platy copper powder.
In the present invention, the spherical copper powder is subjected to plate-forming treatment. The flake powder cannot be processed into a plate. In step (1), the spherical copper powder preferably has an average particle diameter of 0.5 to 2.5. mu.m, for example, 0.6. mu.m, 0.8. mu.m, 1. mu.m, 1.2. mu.m, 1.5. mu.m, 1.8. mu.m, 2. mu.m, 2.2. mu.m. The smaller the particle size of the copper powder is, the higher the reactivity is, and after the average particle size of the copper powder is less than 0.5 μm, the excessive reactivity can cause copper diffusion effect at the joint of the MLCC copper electrode and the nickel electrode, so that holes are formed at the joint of the copper electrode and the nickel electrode, the capacitance capacity is reduced, and the High Accelerated Life Test (HALT) performance is deteriorated. When the particle size of the copper powder is larger than 2.5 μm, the sintering temperature is increased, and the electrical properties of the small-size high-capacity MLCC are also influenced.
In the step (1), the nano Ag colloid can be water dispersion or ethanol dispersion of nano Ag, preferably ethanol dispersion, which is beneficial to realizing uniform coating. The mass concentration of Ag in the nano Ag colloid is preferably 5000-10000ppm, such as 6000ppm and 8000ppm, which is beneficial to realizing uniform coating. The particle size range of the nano Ag is preferably 10-30nm, which is beneficial to realizing uniform coating on the surface of the copper powder. Stable nano-Ag colloids suitable for use in the present invention are commercially available.
The binder for preparing the nano Ag/spherical copper powder slurry comprises resin and an organic solvent. The resin in the binder may be an acrylic resin. The number average molecular weight of the acrylic resin may be 20 to 60 ten thousand, for example 30 ten thousand, 35 ten thousand, 40 ten thousand, 45 ten thousand, 50 ten thousand. The organic solvent in the binder may be one or more selected from octanol, terpineol, hydrogenated terpineol, and the like. In some embodiments, the organic solvent in the binder consists of terpineol and hydrogenated terpineol, which may be present in a mass ratio of 2:1 to 2:2, e.g., 1: 1. The resin content of the binder may be 30wt% to 50wt%, for example 35wt%, 38wt%, 40wt%, 42wt%, 45 wt%.
The dispersant used to prepare the nano-Ag/spherical copper powder slurry may be ethanol.
In the step (1), the mass ratio of the spherical copper powder to the nano Ag colloid is preferably 100 (8-12), for example 100: 10. The mass ratio of the spherical copper powder to the binder is preferably 100 (3-10), for example, 100:5 or 100: 7. The mass ratio of the spherical copper powder to the dispersant is preferably 100 (70-80), for example 100: 75. The copper powder content of the nano-Ag/spherical copper powder slurry prepared in step (1) is preferably 50wt% to 55wt%, for example 51wt%, 52wt%, 53wt%, 54 wt%.
In step (1), the linear velocity of mixing is preferably 40 to 60m/s, for example 50m/s, which is advantageous for achieving uniform mixing and coating. Mixing can be carried out using a high-speed mixer capable of achieving a linear speed of 40-60 m/s. The mixing time is preferably 0.5-1.5h, e.g. 1 h.
In the step (2), the nano Ag/spherical copper powder slurry is stirred and ground at a low speed by using a grinder, so that the grinding medium impacts the copper powder at a low speed, and the platy treatment of the spherical powder is realized. The grinding media are preferably zirconia beads in the diameter range of 0.28-0.32 mm. The loading of the grinding media is preferably 30 to 40%, for example 35%, of the capacity of the mill. The invention realizes the treatment of platy copper powder by impacting spherical copper powder with a preferred grinding medium and a filling amount. When the particle size of the grinding medium is selected to be too large, the impact force on the copper powder is too large, so that the copper powder is easily flaked rather than formed into a platy copper powder, and when the particle size of the grinding medium is smaller, the impact force on the copper powder is smaller, so that the spherical copper powder cannot be deformed. When the filling amount is too small, the copper powder becomes uneven in plate shape, and when the filling amount is too large, the copper powder tends to be formed into a plate shape rather than a plate shape.
In the step (2), the rotating speed of the grinder is preferably 60-80rpm/min, for example 70rpm/min, which is beneficial to ensuring the uniformity of the platy treatment of the nano Ag/spherical copper powder slurry. The stirring time is preferably from 0.5 to 1.5h, for example 1 h.
In the step (2), after the plate-like treatment, low-temperature baking treatment is performed to remove the dispersing agent, and then heat treatment in an inert gas atmosphere is performed to stably coat the plate-like copper powder with the nano-Ag. The temperature of the low-temperature baking is preferably 80 to 100 c, for example 90 c. The incubation time for the low temperature bake is preferably 4-6h, e.g. 5 h. The temperature of the inert gas atmosphere heat treatment is preferably 150 ℃ to 250 ℃, for example 200 ℃. The heat treatment time is preferably 1-2h, for example 1.5 h. The pressure of the inert gas atmosphere is preferably 0.002 to 0.008MPa, for example, 0.005 MPa. The inert gas may be nitrogen.
In some embodiments, the nano-Ag coated platy copper powder is prepared using a method comprising:
(1) mixing spherical copper powder, nano Ag colloid, a binder and ethanol by a high-speed mixer to obtain uniformly dispersed nano Ag/spherical copper powder slurry;
(2) stirring the uniformly dispersed nano Ag/spherical copper powder slurry at a low speed through a grinder to enable a grinding medium to impact the copper powder at a low speed, so as to realize platy treatment of the ball powder, and baking at a low temperature to volatilize ethanol and performing heat treatment in a nitrogen atmosphere to obtain nano Ag coated platy copper powder with the thickness of 0.3-1.5 mu m;
glass powder
The glass powder suitable for the invention is B-Si-Zn-Al-Nb system glass powder, and the raw materials comprise the following components in percentage by weight: b is 2 O 3 32-35％，SiO 2 21-28％，ZnO 20-22％，Al 2 O 3 16-18% of NbO 3-5%. The invention adopts reduction B 2 O 3 Content of SiO is increased 2 The formula of the glass powder with the content reduces Ts (softening temperature) of the glass powder from 600 ℃ to 550 ℃, thereby being more matched with the characteristic of low-temperature sintering of copper paste prepared by coating the plate-shaped copper powder with the nano Ag. The glass frit suitable for use in the present invention preferably has an average particle diameter of 1 to 2.5. mu.m, for example, 1.3. mu.m, 1.5. mu.m, 1.7. mu.m, 2 μm.
Resin and organic solvent
The resin in the copper termination paste may be an acrylic resin. The number average molecular weight of the acrylic resin may be 20 to 60 ten thousand, for example 30 ten thousand, 35 ten thousand, 40 ten thousand, 45 ten thousand, 50 ten thousand. The organic solvent in the copper-terminated electrode paste may be one or more selected from octanol, terpineol, hydrogenated terpineol, and the like. In some embodiments, the organic solvent consists of terpineol and hydrogenated terpineol, which may be present in a mass ratio of 2:1 to 2:2, e.g., 1: 1.
In some embodiments, the resin is dissolved in a portion of the organic solvent to obtain a binder, and the nano-Ag coated copper flake, the glass powder, the binder, and the remaining organic solvent are mixed to obtain the copper end electrode paste. The resin content of the binder may be 30wt% to 50wt%, for example 35wt%, 38wt%, 40wt%, 42wt%, 45 wt%.
Copper end electrode slurry
And uniformly mixing all the components of the copper end electrode slurry, and rolling to obtain the copper end electrode slurry. The copper terminal electrode paste disclosed by the invention preferably comprises nano Ag-coated platy copper powder, glass powder, resin and an organic solvent in a mass ratio of 100 (8-16): (6-12): 25-40). For example, the mass ratio of the plate-shaped nano-Ag-coated copper powder to the glass powder may be 100:10, 100:12, or 100:14, the mass ratio of the plate-shaped nano-Ag-coated copper powder to the resin may be 100:8, 100:9, 100:9.2, 100:9.5, or 100:10, and the mass ratio of the plate-shaped nano-Ag-coated copper powder to the organic solvent may be 100:27, 100:30, 100:31.8, 100:33, or 100: 35. In the copper termination electrode paste according to the present invention, the total content of the nano-Ag-coated plate-like copper powder and the glass powder is preferably 68 to 80wt%, for example, 70wt%, 72wt%, 74wt%, 76wt%, 78 wt%.
In some embodiments, the resin is dissolved in a part of organic solvent to obtain the binder, and then the nano-Ag coated plate-shaped copper powder, the glass powder, the binder and the remaining organic solvent are uniformly mixed and then rolled and dispersed by a three-roll mill to obtain the copper end electrode paste of the present invention. The resin content of the binder may be 30wt% to 50wt%, e.g. 35wt%, 38wt%, 40wt%, 42wt%, 45 wt%. The mass ratio of the nano Ag coated plate-shaped copper powder, the glass powder, the binder and the organic solvent is preferably 100: (10-14): (20-25): (15-20).
Preferably, the homogeneously mixed material is rolled to below 7 μm.
MLCC
The copper end electrode slurry can be used for preparing a copper end electrode of an MLCC. The copper end electrode slurry of the invention can be prepared into the copper end electrode of the MLCC by adopting the conventional process in the field, for example, the copper end electrode slurry is wrapped at the two ends of the MLCC porcelain by a copper bonding machine, and then the glue removal sintering is carried out in a chain sintering furnace under the nitrogen atmosphere, thus obtaining the copper end electrode. One of the characteristics of the copper end electrode slurry of the invention is that the dense sintering can be realized at lower sintering temperature (700-750 ℃).
Preparation principle of nano Ag coated plate-shaped copper powder
The nano Ag colloid consists of dispersed phase particles with the highly dispersed particle size range of 10-30nm and a liquid phase continuous phase. The high-speed mixer which can provide the linear speed of 40-60m/s is adopted to realize the uniform dispersion of the nano Ag colloid and the copper powder in the dispersant (such as ethanol), and the network structure formed by the mutual connection of the high molecular weight molecular chains of the added acrylic resin binder is stable, so that the nano Ag/spherical copper powder slurry is uniformly dispersed by the high-speed mixer.
When the copper powder is platy, the traditional sand mill and wet ball mill have the characteristics of high rotating speed and high filling amount, and the grinding medium is easy to directly smash the spherical copper powder into slices; however, when a grinding medium is added to a conventional stirring and dispersing machine to form a plate, a large amount of non-platelike spherical powder is present. According to the invention, the grinder which is provided with three independent stirring rods and can be used for preparing electronic slurry is adopted to grind and disperse at 60-80rpm/min, the use of the grinder realizes uniform stirring at low speed, the uniformity of platy treatment of the nano Ag/spherical copper powder slurry is ensured, and meanwhile, small-particle-size zirconia balls of 0.08-0.12mm are preferably matched as grinding media, compared with a sand grinder and a wet ball mill, the grinder has weak impact force on spherical copper powder, and platy treatment of the copper powder with thick middle and thin two sides can be realized.
And finally, preserving the heat at 80-100 ℃ for 4-6h to completely volatilize the ethanol, and performing heat treatment at the preferable temperature of 150-250 ℃ in nitrogen atmosphere for 1-2h to avoid the agglomeration of the copper powder and simultaneously form solid solution diffusion between the nano Ag and the plate-shaped copper powder, improve the binding force between the nano Ag and the plate-shaped copper powder, avoid the mechanical dispersion action of a rolling mill to strip the nano Ag from the plate-shaped copper powder, and ensure the effect of the nano Ag on reducing the sintering temperature. The safety of the production process can be ensured by adopting two steps of operation of firstly drying at low temperature and then carrying out nitrogen atmosphere heat treatment.
The invention has the following advantages:
(1) according to the invention, spherical copper powder, a nano Ag colloid, a dispersing agent and a binder are stirred at a low speed by a grinder to enable zirconium oxide beads to impact the spherical copper powder at a low speed, so that platy treatment of the spherical copper powder is realized, and the nano Ag coated platy copper powder is obtained by low-temperature baking and volatilizing ethanol and heat treatment in an inert gas atmosphere. Compared with spherical-sheet mixed copper powder, the prepared copper-end electrode slurry has higher compactness after sintering.
(2) The copper paste prepared by coating the plate-shaped copper powder with the nano Ag forms a Cu-Ag solid phase structure during high-temperature sintering, so that the melting temperature is reduced, and simultaneously, the silver plays a bridging role in the sintering process of the copper powder, thereby being beneficial to sintering. The nano Ag colloid is used as a silver source of the silver-coated plate-shaped copper powder, so that the activity is higher, and the sintering temperature is reduced more obviously. The copper end electrode slurry for the MLCC can be sintered and compacted at the temperature of 700-750 ℃, so that the sintering temperature of the traditional copper end electrode slurry for the MLCC is reduced.
Under the combined action of the two points, the copper-end electrode slurry prepared by the method has high compactness and low sintering temperature (700 ℃ and 750 ℃), and meets the requirements of small-size high-capacity MLCC (multilayer ceramic capacitor) on copper slurry.
The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The following examples use instrumentation conventional in the art. The following examples are given without reference to specific conditions, generally according to conventional conditions, or according to conditions recommended by the manufacturer. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art.
The powder raw materials used in the examples and comparative examples are shown in table 1. Wherein the ratio of the thickness of the spherical copper powder used in examples 1 to 3 and comparative example 1 to the minor axis diameter thereof was higher than 80%, and the ratio of the thickness of the flake copper powder used in comparative example 1 to the minor axis diameter thereof was lower than 5%.
Table 1: powder raw materials used in examples and comparative examples
The organic materials used in the examples and comparative examples are shown in table 2.
Table 2: organic materials used in examples and comparative examples
Example 1
The embodiment of preparing the copper terminal electrode slurry for the small-size high-capacity MLCC specifically comprises the following steps:
(1) preparing nano Ag/spherical copper powder slurry:
spherical copper powder with the average particle size of 0.8 mu m, nano-Ag colloid, a binder and ethanol are mixed for 1.5 hours at the linear speed of 60m/s of a high-speed mixer according to the mass ratio of 100:12:10:80 to obtain uniformly dispersed nano-Ag/spherical copper powder slurry with the copper powder mass fraction of 50%;
(2) preparing nano Ag coated plate-shaped copper powder:
adding the nano Ag/spherical copper powder slurry obtained in the step (1) into a grinder, adding a zirconium oxide grinding medium which accounts for 40% of the volume of the grinder and has a diameter of 0.28-0.32mm, and stirring at 80rpm/min for 1.5h to obtain a nano Ag coated platy copper powder slurry with the copper powder mass fraction of 50%; baking at 80 ℃ for 6h to completely volatilize ethanol, and performing heat treatment at 150 ℃ under 0.008MPa nitrogen atmosphere for 2h to obtain nano Ag-coated platy copper powder, wherein the ratio of the thickness to the short shaft diameter of the nano Ag-coated platy copper powder is 20-60%;
(3) preparation of copper end electrode slurry for small-size high-capacity MLCC:
and (3) uniformly stirring the nano Ag-coated platy copper powder obtained in the step (2), glass powder, a binder and an organic solvent according to the mass ratio of 100:10:20:15, and rolling the mixture in a rolling mill until the fineness is less than 7 mu m to obtain the copper end electrode slurry with the sum of the mass fractions of the nano Ag-coated platy copper powder and the glass powder of 75.86wt% and the sintering densification temperature of 700 ℃.
Example 2
The embodiment of preparing the copper terminal electrode slurry for the small-size high-capacity MLCC specifically comprises the following steps:
(1) preparing nano Ag/spherical copper powder slurry:
mixing spherical copper powder with the average particle size of 1 mu m, nano-Ag colloid, a binder and ethanol for 1h at a high-speed mixer linear speed of 50m/s according to a mass ratio of 100:10:7:75 to obtain uniformly dispersed nano-Ag/spherical copper powder slurry with the copper powder mass fraction of 52%;
(2) preparing nano Ag coated plate-shaped copper powder:
adding the nano Ag/spherical copper powder slurry obtained in the step (1) into a grinder, adding a zirconia grinding medium which accounts for 35% of the volume of the grinder and has the diameter of 0.28-0.32mm, and stirring at 70rpm/min for 1h to obtain nano Ag coated platy copper powder slurry with copper powder mass fraction of 52%; baking at 90 deg.C for 5h to completely volatilize ethanol, and heat treating at 200 deg.C under 0.005MPa nitrogen atmosphere for 1.5h to obtain nanometer Ag coated plate-shaped copper powder, wherein SEM photograph is shown in FIG. 2, and the ratio of thickness to minor axis diameter is 20-60%;
(3) preparing copper end electrode slurry for small-size high-capacity MLCC:
and (3) uniformly stirring the nano Ag coated platy copper powder obtained in the step (2), the glass powder, the binder and the organic solvent according to the mass ratio of 100:12:23:18, and rolling the mixture in a rolling mill until the fineness is below 7 mu m to obtain the copper end electrode slurry with the sum of the mass fractions of the nano Ag coated platy copper powder and the glass powder of 73.20wt% and the sintering densification temperature of 720 ℃.
Example 3
The embodiment of preparing the copper terminal electrode slurry for the small-size high-capacity MLCC specifically comprises the following steps:
(1) preparing nano Ag/spherical copper powder slurry:
spherical copper powder with the average particle size of 2 mu m, nano Ag colloid, a binder and ethanol are mixed for 0.5h at the linear speed of 40m/s of a high-speed mixer according to the mass ratio of 100:8:3:70 to obtain uniformly dispersed nano Ag/spherical copper powder slurry with the mass fraction of the copper powder of 55 percent;
(2) preparing nano Ag coated plate-shaped copper powder:
adding the nano Ag/spherical copper powder slurry obtained in the step (1) into a grinder, adding a zirconium oxide grinding medium which accounts for 30% of the volume of the grinder and has a diameter of 0.28-0.32mm, and stirring for 0.5h at a speed of 60pm/min to obtain nano Ag coated platy copper powder slurry with copper powder mass fraction of 55%; baking at 100 ℃ for 4h to completely volatilize ethanol, and performing heat treatment at 250 ℃ under 0.002MPa nitrogen atmosphere for 1h to obtain the nano Ag-coated platy copper powder, wherein the ratio of the thickness to the short axis diameter of the nano Ag-coated platy copper powder is 20-60%;
(3) preparation of copper end electrode slurry for small-size high-capacity MLCC:
and (3) uniformly stirring the nano Ag coated platy copper powder obtained in the step (2), the glass powder, the binder and the organic solvent according to the mass ratio of 100:14:25:20, and rolling the mixture in a rolling mill until the fineness is less than 7 microns to obtain the copper end electrode slurry with the sum of the mass fractions of the nano Ag coated platy copper powder and the glass powder of 71.70wt% and the sintering densification temperature of 750 ℃.
Comparative example 1
The comparative example provides copper-terminated electrode paste for MLCC, which is prepared by mixing flake copper powder and spherical copper powder, and specifically comprises the following steps:
(1) preparing nano Ag/sheet ball copper powder slurry:
mixing flake copper powder with the average particle size of 1 mu m, spherical copper powder with the average particle size of 1 mu m, nano Ag colloid, a binder and ethanol for 1h at the linear speed of a high-speed mixer of 50m/s according to the mass ratio of 70:30:10:7:75 to obtain uniformly dispersed nano Ag/flake spherical copper powder slurry with the mass fraction of the copper powder of 52%;
(2) preparing nano Ag-coated sheet ball copper powder:
baking the nano Ag/flake copper powder slurry obtained in the step (1) at 90 ℃ for 5h to completely volatilize ethanol, and performing heat treatment at 0.005MPa in nitrogen atmosphere at 200 ℃ for 1.5h to obtain nano Ag-coated flake copper powder;
(3) preparing copper-terminated electrode slurry for MLCC:
and (3) mixing the nano Ag coated sheet ball copper powder obtained in the step (2), glass powder, a binder and an organic solvent according to a mass ratio of 100:12:23:18, stirring uniformly, and rolling to the fineness of less than 7 mu m in a rolling mill to obtain copper end electrode slurry with the sum of the mass fractions of the nano Ag-coated sheet spherical copper powder and the glass powder of 73.20wt% and the sintering densification temperature of 720 ℃.
Test example
The copper end electrode paste prepared in comparative example 1 was wrapped on both ends of an MLCC porcelain (model: 0201) by a copper bonding machine, binder removal sintering was performed at a maximum temperature of 720 ℃ in a nitrogen atmosphere chain sintering furnace, the maximum temperature was maintained for 10min, and SEM observation was performed on the end face and cross section of the copper end electrode after sintering, and the results are shown in fig. 3 and 4. The copper end electrode slurry prepared in example 2 was wrapped on both ends of an MLCC porcelain (model: 0201) by a copper bonding machine, binder removal sintering was performed at a maximum temperature of 720 ℃ in a nitrogen atmosphere chain sintering furnace, the maximum temperature was maintained for 10min, and SEM observation was performed on the end face and cross section of the copper end electrode after sintering, and the results are shown in fig. 5 and 6.
As can be seen from fig. 3 and 4, in comparative example 1, the copper termination electrode paste for MLCC prepared by mixing copper powder with the nano Ag-coated pellet ball was sintered at 720 ℃ and had pores on the surface and inside. As can be seen from fig. 5 and 6, the copper termination electrode paste for small-sized high-capacity MLCC prepared by coating the plate-shaped copper powder with nano Ag in example 2 has high compactness after sintering at a maximum temperature of 720 ℃, and has no pores on the surface and inside. The results show that the copper end electrode slurry prepared by coating the plate-shaped copper powder with the nano Ag has higher sintering compactness than the copper end electrode slurry prepared by mixing the nano Ag coated sheet ball with the copper powder.
Claims (9)
1. The copper end electrode slurry for the multilayer chip ceramic capacitor is characterized by comprising the following components in percentage by mass: (8-16): (6-12): (25-40) coating the plate-shaped copper powder with the nano Ag, the glass powder, the resin and the organic solvent, wherein the thickness of the plate-shaped copper powder coated with the nano Ag is 0.3-1.5 mu m, and the ratio of the thickness of the plate-shaped copper powder coated with the nano Ag to the minor axis diameter is 5% -80%;
the nano Ag-coated platy copper powder is prepared by adopting a method comprising the following steps of:
(1) uniformly mixing spherical copper powder, nano Ag colloid, binder and dispersant to obtain nano Ag/spherical copper powder slurry;
(2) and stirring and grinding the nano Ag/spherical copper powder slurry by using a grinder, and then performing baking treatment and inert gas atmosphere heat treatment to obtain the nano Ag coated platy copper powder.
2. The copper terminal electrode paste for a multilayer chip ceramic capacitor according to claim 1, wherein the ratio of the thickness of the nano-Ag coated plate-like copper powder to the minor axis diameter is 20 to 60%.
3. The copper termination electrode paste for a multilayer chip ceramic capacitor according to claim 1, wherein the copper termination electrode paste for a multilayer chip ceramic capacitor has one or more of the following characteristics:
in the step (1), the average grain diameter of the spherical copper powder is 0.5-2.5 μm;
in the step (1), the mass concentration of the nano Ag in the nano Ag colloid is 5000-10000ppm, and the particle size of the nano Ag is 10-30 nm;
in the step (1), the binder comprises a resin and an organic solvent;
in the step (1), the dispersant is ethanol;
in the step (1), the mass ratio of the spherical copper powder, the nano Ag colloid, the binder and the dispersant is 100: (8-12): (3-10): (70-80);
in the step (1), the linear speed of mixing is 40-60m/s, and the mixing time is 0.5-1.5 h;
in the step (2), the rotating speed of the mill is 60-80rpm/min, and the stirring time is 0.5-1.5 h;
in the step (2), zirconia beads with the diameter of 0.28-0.32mm are adopted as grinding media by the grinder;
in the step (2), adding grinding media which account for 30-40% of the volume of the grinder into the grinder;
in the step (2), the baking temperature is 80-100 ℃, and the baking time is 4-6 h;
in the step (2), the temperature of the inert gas atmosphere heat treatment is 150-;
in the step (2), the inert gas is nitrogen.
4. The copper termination electrode paste for a multilayer chip ceramic capacitor according to claim 3, wherein the copper termination electrode paste for a multilayer chip ceramic capacitor has one or more of the following characteristics:
in the binder, the resin is acrylic resin;
in the binder, the organic solvent is selected from one or more of octanol, terpineol and hydrogenated terpineol;
in the binder, the mass fraction of the resin is 35-45%.
5. The copper termination electrode paste for a multilayer chip ceramic capacitor according to claim 1, wherein the copper termination electrode paste for a multilayer chip ceramic capacitor has one or more of the following characteristics:
the glass powder comprises the following raw materials in percentage by weight: b is 2 O 3 32-35％，SiO 2 21-28％，ZnO 20-22％，Al 2 O 3 16-18％，NbO 3-5％；
The average grain diameter of the glass powder is 1-2.5 μm;
the resin is acrylic resin;
the organic solvent is selected from one or more of octanol, terpineol and hydrogenated terpineol;
the mass ratio of the nano Ag coated plate-shaped copper powder to the glass powder to the resin to the organic solvent is 100: (10-14): (7.5-10.5): (26-36).
6. A method of preparing the copper terminal electrode paste for a multilayer chip ceramic capacitor according to any one of claims 1 to 5, comprising: and dispersing the resin in a part of organic solvent to obtain a binder, uniformly mixing the nano Ag coated plate-shaped copper powder, the glass powder, the binder and the rest of organic solvent, and rolling by using a rolling mill until the fineness reaches below 7 mu m to obtain the copper end electrode slurry for the multilayer chip ceramic capacitor.
7. A multilayer chip ceramic capacitor comprising copper terminal electrodes prepared using the copper terminal electrode paste for a multilayer chip ceramic capacitor according to any one of claims 1 to 5.
8. A plate-like copper powder coated with nano Ag, wherein the plate-like copper powder coated with nano Ag is according to any one of claims 1 to 4.
9. A method for lowering the sintering temperature of or improving the sintering compactness of copper terminal electrode paste for a multilayer chip ceramic capacitor, comprising adding the nano Ag-coated plate-like copper powder according to claim 8 to the copper terminal electrode paste for a multilayer chip ceramic capacitor.
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