CN117711813A - Nickel inner electrode slurry for small-size MLCC and preparation method thereof - Google Patents
Nickel inner electrode slurry for small-size MLCC and preparation method thereof Download PDFInfo
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- CN117711813A CN117711813A CN202311870203.1A CN202311870203A CN117711813A CN 117711813 A CN117711813 A CN 117711813A CN 202311870203 A CN202311870203 A CN 202311870203A CN 117711813 A CN117711813 A CN 117711813A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 78
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 58
- 230000000996 additive effect Effects 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 52
- 239000000919 ceramic Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000000080 wetting agent Substances 0.000 claims abstract description 18
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 26
- 239000002003 electrode paste Substances 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 5
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims description 4
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 3
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 3
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- VAWSWDPVUFTPQO-UHFFFAOYSA-N calcium strontium Chemical compound [Ca].[Sr] VAWSWDPVUFTPQO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 238000005336 cracking Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 239000012776 electronic material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000843 powder Substances 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- -1 firstly Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Ceramic Capacitors (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to a functional electronic material, and discloses a nickel inner electrode slurry for small-size MLCC and a preparation method thereof, wherein the nickel inner electrode slurry comprises the following raw materials in parts by weight: 45-60 parts of nickel powder, 5-10 parts of modified ceramic additive, 6-7 parts of organic resin, 3-6 parts of wetting agent, 0.5-2 parts of stabilizer and 20-30 parts of solvent; the nickel powder is spherical-like nickel powder with the average particle size of 80-200 nm, and the organic resin is polyvinyl butyral resin; the nickel internal electrode slurry for small-size MLCC contains particles with the particle size smaller than 0.4 μm. The chip cracking phenomenon of the sintered small-size MLCC product can be prevented, so that the breakdown phenomenon of the small-size MLCC product in use is reduced; the printing surface is smooth, no agglomerated particles exist, and the pressure resistance value can meet the requirements of corresponding specifications.
Description
Technical Field
The invention relates to a functional electronic material, in particular to nickel internal electrode slurry for small-size MLCC and a preparation method thereof.
Background
Chip multilayer ceramic capacitors (MLCCs) are important electronic components, mainly used in the fields of mobile phones, 5G communications, automotive electronics, and the like.
With the rise of domestic high-end 5G mobile phones, MLCC products have larger development demands, and the domestic demands of future MLCCs are increasing. 1500-1600 small-sized MLCCs are needed for each high-end mobile phone.
The small-sized MLCC refers to a chip type multilayer ceramic capacitor commonly known in the industry as imperial 0201, 0402 or 0603.
The MLCC is composed of an inner electrode, a ceramic layer and an end electrode, wherein dielectric materials and the inner electrode are stacked in a staggered mode and then sintered at high temperature to form a block, and the end electrode is a metal layer sealed at two ends of the block.
The nickel inner electrode slurry is a main material for manufacturing an inner electrode, the nickel inner electrode slurry in the prior art mainly depends on import, and when the nickel inner electrode slurry produced in China is adopted to prepare the small-size MLCC, the nickel inner electrode slurry has poor printing performance, a sintered chip is easy to crack, and the defect of low pressure resistance exists.
Disclosure of Invention
In view of the above problems, a first object of the present invention is to propose a nickel internal electrode paste for small-sized MLCCs, which can prevent chip cracking of sintered products and has good printing performance.
The second aim of the invention is to provide a preparation method of the nickel inner electrode slurry, which can prevent powder from agglomerating in the production process and the storage and transportation process.
To achieve the purpose, the invention adopts the following technical scheme:
the nickel internal electrode slurry for the small-size MLCC comprises the following raw materials in parts by weight:
45-60 parts of nickel powder, 5-10 parts of modified ceramic additive, 6-7 parts of polyvinyl butyral resin, 3-6 parts of wetting agent, 0.5-2 parts of stabilizer and 20-30 parts of solvent;
the nickel powder is spherical-like nickel powder with the average particle size of 80nm-200 nm;
the nickel internal electrode slurry for small-size MLCC contains particles with the particle size smaller than 0.4 μm.
Further, the surface of the nickel powder is provided with an oxide layer, and the thickness of the oxide layer is more than 5nm; the particle Dmax of the nickel powder is less than or equal to 700nm.
Preferably, the modified ceramic additive is a mixture of a ceramic additive and a modifying additive;
the ceramic additive comprises at least one of barium titanate, calcium titanate, strontium titanate, barium zirconate titanate and calcium strontium zirconate;
the modifying additive comprises at least one of lanthanum oxide, cerium oxide and dysprosium oxide;
the modifying additive accounts for 1% -5% of the total mass of the ceramic additive.
Preferably, the average particle diameter of the ceramic additive is 30nm-80nm, and the particle Dmax of the ceramic additive is less than 150nm;
the particle size of the modified additive is less than 50nm.
Preferably, the wetting agent is an alkane low solubility solvent.
Preferably, the stabilizer includes at least one of acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid and caproic acid.
Preferably, the solvent includes at least one of cyclic ethanol acetate, methyl acetate, ethyl acetate, terpineol, n-propanol, dipropylene glycol dimethyl ether, and hydrogenated terpineol.
Further, the invention provides a preparation method of the nickel inner electrode slurry, which is used for preparing the nickel inner electrode slurry for the small-size MLCC and comprises the following steps of:
s1) respectively weighing nickel powder, a modified ceramic additive, polyvinyl butyral resin, a wetting agent, a stabilizer and a solvent according to a set mass percentage;
s2) adding polyvinyl butyral resin and a wetting agent into a planetary mixer, dispersing for 1-2 hours at the rotation speed of 900-1000rpm and the temperature of 70-90 ℃, and filtering by using 200-mesh filter cloth to prepare an organic carrier dispersion;
s3) adding the modified ceramic additive into a planetary mixer, and dispersing for 2-4 hours at the rotating speed of 250-500rpm to prepare a co-material primary dispersion;
s4) adding the first dispersion of the co-materials into a three-roller mill, shearing and dispersing for 1-1.5h at the rotating speed of 400-600rpm to prepare a second dispersion of the co-materials;
s5) respectively adding nickel powder and solvent into a circulating dispersing machine, and emulsifying and dispersing for 2-3 hours at a rotating speed of 2000-3000rpm to prepare nickel powder dispersion;
s6) adding the organic carrier dispersion, the co-material secondary dispersion and the nickel powder dispersion into a high-speed dispersion machine, and dispersing for 1-2 hours at a rotating speed of 3000-4000rpm to prepare a nickel slurry mixture;
s7) using a three-roller mill to carry out dispersion treatment on the nickel paste mixture at the rotating speed of 400-600rpm for 2-3 hours, and filtering to obtain the nickel inner electrode paste.
Preferably, in step S5), the circulation dispersion machine includes a plurality of stator and rotor, the gap lamination between the stator and rotor is less than 1mm, and the rotation speed of the stator and rotor is 3500rpm.
Preferably, in step S7), the pore size of the filter element is 0.4 μm and the filtration pressure is 0.1-0.2MPa.
The technical scheme of the invention has the beneficial effects that: the adopted spherical-like nickel powder with the average particle size of 80-200 nm is used as a binder, and the polyvinyl butyral resin is used as the binder to reduce the carbon content of residues formed after sintering of the binder so as to improve the compactness of the filler of the nickel inner electrode slurry for the small-size MLCC in the pores of the dielectric layer, thereby preventing the chip cracking phenomenon of the sintered small-size MLCC product and reducing the breakdown phenomenon of the small-size MLCC product during use; the printing surface is smooth, no agglomerated particles exist, and the pressure resistance value can meet the requirements of corresponding specifications.
According to the preparation method of the nickel inner electrode slurry, firstly, metal powder, a common material and an adhesive are respectively subjected to dispersion treatment, then the dispersed metal powder, the common material and the adhesive are mixed for rolling dispersion, agglomeration of the powder in the production process and the storage process is avoided, dispersion stability of the prepared nickel inner electrode slurry is improved, printing performance of the nickel inner electrode slurry for small-size MLCC is guaranteed, and yield of the nickel inner electrode slurry is improved.
Drawings
FIG. 1 is a 200x view under a microscope of the slurry membrane prepared in example 1;
FIG. 2 is a 200x view under a microscope of the slurry membrane prepared in example 2;
FIG. 3 is a photograph of a pattern of the nickel internal electrode paste of example 1 after printing under a 200X microscope;
FIG. 4 is a photograph of a pattern of the nickel inner electrode paste of example 2 after printing under a 200X microscope;
FIG. 5 is a 200x view under a microscope of the slurry film sheet prepared in comparative example 1;
FIG. 6 is a photograph of a pattern of the nickel inner electrode paste of comparative example 1 after printing under a 200X microscope;
FIG. 7 is a DPA chip analysis photograph of a broken down MLCC chip of comparative example 1;
fig. 8 is a photograph of a DPA grind chip of the broken down MLCC chip of comparative example 2.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
In the description herein, reference to the term "embodiment," "example," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
The nickel internal electrode slurry for the small-size MLCC comprises the following raw materials in parts by weight:
45-60 parts of nickel powder, 5-10 parts of modified ceramic additive, 6-7 parts of polyvinyl butyral resin, 3-6 parts of wetting agent, 0.5-2 parts of stabilizer and 20-30 parts of solvent;
the nickel powder is spherical-like nickel powder with the average particle size of 80nm-200 nm;
the nickel internal electrode slurry for small-size MLCC contains particles with the particle size smaller than 0.4 μm.
According to the nickel inner electrode slurry for the small-size MLCC, the spherical-like nickel powder with the average particle size of 80-200 nm is adopted, and the polyvinyl butyral resin is used as the binder, so that the carbon content of residues formed after sintering of the binder is reduced, the particle size of particles in the slurry is less than 0.4 mu m, the compactness of the filler of the nickel inner electrode slurry for the small-size MLCC in the pores of the dielectric layer can be improved, and the chip cracking phenomenon of the sintered small-size MLCC product is prevented, and the breakdown phenomenon of the small-size MLCC product in use is reduced; the printing surface is smooth, no agglomerated particles exist, and the pressure resistance value can meet the requirements of corresponding specifications.
Further, the surface of the nickel powder is provided with an oxide layer, and the thickness of the oxide layer is more than 5nm; the particle Dmax of the nickel powder is less than or equal to 700nm.
If nickel powder with the particle Dmax more than 700nm is adopted, the difficulty of preparing the nickel inner electrode slurry with the particle diameter less than 0.4 mu m is high, the production cost is high, the yield is low, the production efficiency is low, and the average particle diameter of the particles contained in the nickel inner electrode slurry is easy to be larger, so that the phenomenon that the small-size MLCC product is broken down when in use is caused.
The thickness of the oxide layer on the surface of the nickel powder is more than 5nm, so that the crystallization performance of the nickel powder after sintering can be improved, the sintered small-size MLCC has higher mildness, and the phenomenon of chip cracking of the small-size MLCC is further avoided.
Preferably, the modified ceramic additive is a mixture of a ceramic additive and a modifying additive;
the ceramic additive comprises at least one of barium titanate, calcium titanate, strontium titanate, barium zirconate titanate and calcium strontium zirconate;
the modifying additive comprises at least one of lanthanum oxide, cerium oxide and dysprosium oxide;
the modifying additive accounts for 1% -5% of the total mass of the ceramic additive.
The ceramic additive and the modified additive in the modified ceramic additive form a core-shell structure during sintering, so that the electric properties of the sintered small-size MLCC, such as capacitance, voltage resistance, insulation resistance and the like, can be improved.
Preferably, the average particle diameter of the ceramic additive is 30nm-80nm, and the particle Dmax of the ceramic additive is less than 150nm;
the particle size of the modified additive is less than 50nm.
By adopting the ceramic additive and the modified additive with the particle sizes, the production difficulty and the production cost can be reduced, the production efficiency can be improved, and the sintered small-size MLCC can have better electrical performance.
Preferably, the wetting agent is an alkane low solubility solvent.
The above wetting agent is preferably one of Exxsol series dearomatized solvent oils.
The nickel powder adopted by the nickel inner electrode slurry for the small-size MLCC and the powder of the modified ceramic additive are ultrafine nanoscale powder, so that the surface energy is large and agglomeration is easy to occur. The powder can be wetted by adding a proper amount of the wetting agent, so that the surface energy among the powder is effectively reduced, the agglomeration among the powder is reduced, and the dispersion uniformity of the nickel inner electrode slurry for the small-size MLCC is improved.
Preferably, the stabilizer includes at least one of acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid and caproic acid.
The nickel inner electrode slurry for the small-size MLCC is easy to agglomerate after contacting with water and carbon dioxide in the air, and a proper amount of stabilizer is added, so that the occurrence of agglomeration phenomenon is avoided, and the dispersion uniformity of the nickel inner electrode slurry for the small-size MLCC is maintained.
Preferably, the solvent includes at least one of cyclic ethanol acetate, methyl acetate, ethyl acetate, terpineol, n-propanol, dipropylene glycol dimethyl ether, and hydrogenated terpineol.
The solvent is mainly used for dissolving organic resin, and meets the environmental protection requirement.
Further, the invention provides a preparation method of the nickel inner electrode slurry, which is used for preparing the nickel inner electrode slurry for the small-size MLCC and comprises the following steps of:
s1) respectively weighing nickel powder, a modified ceramic additive, polyvinyl butyral resin, a wetting agent, a stabilizer and a solvent according to a set mass percentage;
s2) adding polyvinyl butyral resin and a wetting agent into a planetary mixer, dispersing for 1-2 hours at the rotation speed of 900-1000rpm and the temperature of 70-90 ℃, and filtering by using 200-mesh filter cloth to prepare an organic carrier dispersion;
s3) adding the modified ceramic additive into a planetary mixer, and dispersing for 2-4 hours at the rotating speed of 250-500rpm to prepare a co-material primary dispersion;
s4) adding the first dispersion of the co-materials into a three-roller mill, shearing and dispersing for 1-1.5h at the rotating speed of 400-600rpm to prepare a second dispersion of the co-materials;
s5) respectively adding nickel powder and solvent into a circulating dispersing machine, and emulsifying and dispersing for 2-3 hours at a rotating speed of 2000-3000rpm to prepare nickel powder dispersion;
s6) adding the organic carrier dispersion, the co-material secondary dispersion and the nickel powder dispersion into a high-speed dispersion machine, and dispersing for 1-2 hours at a rotating speed of 3000-4000rpm to prepare a nickel slurry mixture;
s7) using a three-roller mill to carry out dispersion treatment on the nickel paste mixture at the rotating speed of 400-600rpm for 2-3 hours, and filtering to obtain the nickel inner electrode paste.
According to the preparation method of the nickel inner electrode slurry, the metal powder, the common material and the adhesive are subjected to dispersion treatment, and then the dispersed metal powder, the common material and the adhesive are mixed for rolling dispersion, so that agglomeration of the powder in the production process and the storage process is avoided, the dispersion stability of the prepared nickel inner electrode slurry is improved, the printing performance of the nickel inner electrode slurry for the small-size MLCC is ensured, and the yield of the nickel inner electrode slurry is improved.
Preferably, in step S5), the circulation dispersion machine includes a plurality of stator and rotor, the gap lamination between the stator and rotor is less than 1mm, and the rotation speed of the stator and rotor is 3500rpm.
The circulating dispersion machine has higher shearing force, and can effectively ensure the particle fineness of the prepared nickel powder dispersion, thereby ensuring the yield of the nickel inner electrode slurry with the particle diameter smaller than 0.4 mu m, and further ensuring the printing performance of the nickel inner electrode slurry for small-size MLCC.
Preferably, in step S7), the pore size of the filter element is 0.4 μm and the filtration pressure is 0.1-0.2MPa.
Particulate matter having a particle size greater than 0.4 μm is filtered off by filtration to avoid affecting the flatness of the electrode paste in the printed nickel.
Examples 1-2 and comparative examples 1-2
1. The nickel internal electrode pastes of each example and each comparative example were prepared according to the composition ratios listed in table 1 as follows:
s1) respectively weighing nickel powder, a modified ceramic additive, organic resin, a wetting agent, a stabilizer and a solvent according to the set mass percentage;
s2) adding the organic resin and the wetting agent into a planetary mixer, dispersing for 1-2 hours at the rotation speed of 900-1000rpm and the temperature of 70-90 ℃, and filtering by using 200-mesh filter cloth to prepare an organic carrier dispersion;
s3) adding the modified ceramic additive into a planetary mixer, and dispersing for 2-4 hours at the rotating speed of 250-500rpm to prepare a co-material primary dispersion;
s4) adding the first dispersion of the co-materials into a three-roller mill, shearing and dispersing for 1-1.5h at the rotating speed of 400-600rpm to prepare a second dispersion of the co-materials;
s5) respectively adding nickel powder and solvent into a circulating dispersing machine, and emulsifying and dispersing for 2-3 hours at a rotating speed of 2000-3000rpm to prepare nickel powder dispersion;
s6) adding the organic carrier dispersion, the co-material secondary dispersion and the nickel powder dispersion into a high-speed dispersion machine, and dispersing for 1-2 hours at a rotating speed of 3000-4000rpm to prepare a nickel slurry mixture;
s7) using a three-roller mill to carry out dispersion treatment on the nickel paste mixture at the rotating speed of 400-600rpm for 2-3 hours, and filtering to obtain the nickel inner electrode paste.
In the step S5), the circulating dispersing machine comprises a plurality of stator and rotors, the gap lamination between the stator and the rotor is less than 1mm, and the rotating speed of the stator and the rotor is 3500rpm.
In step S6), the pore diameter of the filter element is 0.4 μm, and the filtering pressure is 0.1-0.2MPa.
The nickel powder is spherical-like nickel powder with the average particle size of 80-200 nm, an oxide layer is arranged on the surface of the nickel powder, and the thickness of the oxide layer is more than 5nm; the Dmax of the particles of the nickel powder is less than 700nm;
the organic resin is polyvinyl butyral resin;
the modified ceramic additive is a mixture of a ceramic additive and a modified additive; the ceramic additive is calcium titanate; the modified additive is dysprosium oxide; the modifying additive accounts for 2% of the total mass of the ceramic additive;
the average particle diameter of the ceramic additive is 30nm-80nm, and the particle Dmax of the ceramic additive is less than 150nm; the particle size of the modified additive is less than 50nm;
the wetting agent is Exxsol-D80 dearomatization solvent oil; the stabilizer is isobutyric acid; the solvent is ethyl acetate.
2. The nickel internal electrode slurry prepared in each example or comparative example was used, whether or not the slurry film had agglomerated particles was observed under a 200-fold microscope, and the slurry was coated on a smooth glass plate using a 5 μm coater, and after drying, the surface roughness was measured using a Mitutoyo SJ410 roughness apparatus of Sanfeng, japan, and the measurement results are shown in Table 1;
3. according to the prior art MLCC preparation process, MLCCs with an imperial size of 0201 were obtained by lamination-cutting-adhesive discharging-sintering, and then electrical properties of MLCCs with an imperial size of 0201 of each example or comparative example were measured using an electrical property tester, and the measurement results are shown in table 1.
TABLE 1 raw material amounts and detection results for examples 1-3 and comparative examples 1-2
According to the experimental results of table 1 above, the analysis is illustrated as follows:
1. the nickel inner electrode paste was prepared with nickel powder having an average particle diameter of 120-200nm in examples 1 and 2, respectively, by controlling Dmax of nickel powder particles while dispersing materials using multiple steps, and the product paste films prepared in examples 1 and 2 were free of agglomerated particles as shown in fig. 1 and 2, respectively, in 200x observation pictures under a microscope, and had small surface roughness as shown in table 1, indicating that the nickel inner electrode paste of examples 1 and 2 was excellent in dispersion; the observation photographs of the patterns of the nickel internal electrode pastes of the example 1 and the example 2 after printing are respectively shown in the figures 3 and 4 under a 200x microscope, the printed patterns are flat, no edge seepage exists, and the printing performance is excellent; the MLCCs of the British system size 0201 of the embodiment 1 and the embodiment 2 have good electric performance and high voltage resistance, and can meet the application requirements of small-size MLCCs.
2. The dispersion method of the nickel internal electrode paste of comparative example 1 is different from that of example 1, and steps S4) and S5) are not included, as shown in a 200x observation photograph under a microscope of fig. 5, the paste film of comparative example 1 has a small amount of agglomerated particles, and the surface roughness of comparative example 1 is larger than that of both examples 1 and 2, indicating that the nickel internal electrode paste of comparative example 1 is not ideal in dispersion effect; the printed pattern of the nickel inner electrode paste of comparative example 1, which was slightly burred and had an unsatisfactory printing effect, was observed under a 200x microscope as shown in fig. 6; the MLCC of comparative example 1, which had a small withstand voltage value and also had an IR breakdown problem, was subjected to DPA lapping analysis as shown in fig. 7, and found to have a cracking phenomenon inside.
3. The Dmax of the nickel powder selected in the comparative example 2 is more than 700nm, the slurry membrane is observed under a 200x microscope to have no agglomerated particles, and the surface roughness is relatively smaller, which indicates that the nickel inner electrode slurry of the comparative example 2 has excellent dispersion; the printing pattern of the nickel inner electrode paste of comparative example 2 is flat, has no edge penetration and has excellent printability; as shown in Table 1, the MLCC of comparative example 2, which had a lower withstand voltage value of the CRF 0201 and also had a slight IR breakdown problem, was subjected to DPA chip grinding analysis as shown in FIG. 8, and internal cracking was also found.
In summary, the nickel internal electrode slurry for the small-size MLCC adopts the sphere-like nickel powder with the average particle size of 80nm-200nm, and uses the polyvinyl butyral resin as the binder, so as to reduce the carbon content of residues formed after sintering of the binder, so as to improve the compactness of the filling body of the nickel internal electrode slurry for the small-size MLCC in the pores of the dielectric layer, thereby preventing the chip cracking phenomenon of the sintered small-size MLCC product, and reducing the breakdown phenomenon of the small-size MLCC product during use; the printing surface is smooth, no agglomerated particles exist, and the pressure resistance value can meet the requirements of corresponding specifications.
Further, in the preparation method of the nickel inner electrode slurry, firstly, the metal powder, the common material and the adhesive are respectively subjected to dispersion treatment, then the dispersed metal powder, the common material and the adhesive are mixed for rolling dispersion, so that agglomeration of the powder in the production process and the storage process is avoided, the dispersion stability of the prepared nickel inner electrode slurry is improved, the printing performance of the nickel inner electrode slurry for the small-size MLCC is ensured, and the yield of the nickel inner electrode slurry is improved.
The technical principle of the present invention is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general principles of the invention and should not be taken in any way as limiting the scope of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of this specification without undue burden.
Claims (10)
1. The nickel inner electrode slurry for the small-size MLCC is characterized by comprising the following raw materials in parts by weight:
45-60 parts of nickel powder, 5-10 parts of modified ceramic additive, 6-7 parts of polyvinyl butyral resin, 3-6 parts of wetting agent, 0.5-2 parts of stabilizer and 20-30 parts of solvent;
the nickel powder is spherical-like nickel powder with the average particle size of 80nm-200 nm;
the nickel internal electrode slurry for small-size MLCC contains particles with the particle size smaller than 0.4 μm.
2. The nickel inner electrode slurry for small-sized MLCCs of claim 1, wherein a surface of said nickel powder has an oxide layer, said oxide layer having a layer thickness > 5nm; the particle Dmax of the nickel powder is less than or equal to 700nm.
3. The nickel-internal electrode slurry for small-sized MLCCs of claim 1, wherein said modified ceramic additive is a mixture of ceramic additives and modifying additives;
the ceramic additive comprises at least one of barium titanate, calcium titanate, strontium titanate, barium zirconate titanate and calcium strontium zirconate;
the modifying additive comprises at least one of lanthanum oxide, cerium oxide and dysprosium oxide;
the modifying additive accounts for 1% -5% of the total mass of the ceramic additive.
4. The nickel-internal electrode slurry for small-sized MLCCs according to claim 3, wherein an average particle size of said ceramic additive is 30nm-80nm, and a particle Dmax of said ceramic additive is < 150nm;
the particle size of the modified additive is less than 50nm.
5. The nickel-in-electrode slurry for small-sized MLCCs of claim 1, wherein said wetting agent is an alkane-based low solubility solvent.
6. The nickel-inner electrode slurry for small-sized MLCCs of claim 1, wherein said stabilizer comprises at least one of acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, and caproic acid.
7. The nickel inner electrode slurry for small-sized MLCCs of claim 1, wherein said solvent comprises at least one of cyclic ethanol acetate, methyl acetate, ethyl acetate, terpineol, n-propanol, dipropylene glycol dimethyl ether, and hydrogenated terpineol.
8. A method for preparing the nickel inner electrode paste for small-sized MLCCs according to any one of claims 1 to 7, comprising the steps of:
s1) respectively weighing nickel powder, a modified ceramic additive, polyvinyl butyral resin, a wetting agent, a stabilizer and a solvent according to a set mass percentage;
s2) adding polyvinyl butyral resin and a wetting agent into a planetary mixer, dispersing for 1-2 hours at the rotation speed of 900-1000rpm and the temperature of 70-90 ℃, and filtering by using 200-mesh filter cloth to prepare an organic carrier dispersion;
s3) adding the modified ceramic additive into a planetary mixer, and dispersing for 2-4 hours at the rotating speed of 250-500rpm to prepare a co-material primary dispersion;
s4) adding the first dispersion of the co-materials into a three-roller mill, shearing and dispersing for 1-1.5h at the rotating speed of 400-600rpm to prepare a second dispersion of the co-materials;
s5) respectively adding nickel powder and solvent into a circulating dispersing machine, and emulsifying and dispersing for 2-3 hours at a rotating speed of 2000-3000rpm to prepare nickel powder dispersion;
s6) adding the organic carrier dispersion, the co-material secondary dispersion and the nickel powder dispersion into a high-speed dispersion machine, and dispersing for 1-2 hours at a rotating speed of 3000-4000rpm to prepare a nickel slurry mixture;
s7) using a three-roller mill to carry out dispersion treatment on the nickel paste mixture at the rotating speed of 400-600rpm for 2-3 hours, and filtering to obtain the nickel inner electrode paste.
9. The method for producing a nickel electrode paste according to claim 8, wherein in step S5), the circulation dispersion machine comprises a plurality of stator/rotor members, the gap between the stator/rotor members is bonded to < 1mm, and the rotation speed of the stator/rotor members is 3500rpm.
10. The method for preparing a nickel electrode slurry according to claim 8, wherein in the step S7), the pore diameter of the filter element is 0.4 μm and the filtration pressure is 0.1 to 0.2MPa.
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