CN113410050A - Nickel electrode composition and preparation method and application thereof - Google Patents
Nickel electrode composition and preparation method and application thereof Download PDFInfo
- Publication number
- CN113410050A CN113410050A CN202110583542.6A CN202110583542A CN113410050A CN 113410050 A CN113410050 A CN 113410050A CN 202110583542 A CN202110583542 A CN 202110583542A CN 113410050 A CN113410050 A CN 113410050A
- Authority
- CN
- China
- Prior art keywords
- nickel
- electrode composition
- nickel electrode
- percent
- ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 241
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 111
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000919 ceramic Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000011267 electrode slurry Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000003985 ceramic capacitor Substances 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 230000002776 aggregation Effects 0.000 claims description 11
- 238000005054 agglomeration Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- FFQALBCXGPYQGT-UHFFFAOYSA-N 2,4-difluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(F)C=C1F FFQALBCXGPYQGT-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- VAWSWDPVUFTPQO-UHFFFAOYSA-N calcium strontium Chemical compound [Ca].[Sr] VAWSWDPVUFTPQO-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 claims 1
- -1 tackifiers Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 22
- 239000011229 interlayer Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 238000004901 spalling Methods 0.000 abstract description 5
- 238000010344 co-firing Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 229910018663 Mn O Inorganic materials 0.000 description 4
- 229910003176 Mn-O Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007545 Vickers hardness test Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000002003 electrode paste Substances 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 2
- 229910019092 Mg-O Inorganic materials 0.000 description 2
- 229910019395 Mg—O Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01G4/30—Stacked capacitors
-
- 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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Capacitors (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a nickel electrode composition and a preparation method and application thereof, wherein the nickel electrode composition comprises the following raw materials: the nickel electrode composition comprises nickel, ceramic and non-nickel metal, wherein the mass percentage of the non-nickel metal in the nickel electrode composition is 1% -3%. According to the invention, other metals with specific contents are added on the basis of nickel, in the co-firing process of the nickel electrode composition and the ceramic dielectric layer, the added non-nickel metal is more easily combined with oxygen under a weak oxidation condition, and a Ni-M-O (M represents non-nickel metal) crystalline phase structure is generated on the interface of Ni and the ceramic, so that on one hand, the oxidation of Ni in the sintering process is prevented, on the other hand, a secondary phase with stronger bonding force is formed on the interface of Ni and the ceramic, the bonding force between the Ni electrode and the dielectric layer is effectively increased by the secondary phase, the interlayer bonding force of I-type MLCC products can be obviously improved, and the product spalling risk is reduced, especially high-capacity and multi-layer products.
Description
Technical Field
The invention relates to the technical field of electronic composite powder and chip multilayer ceramic capacitor electrode materials, in particular to a nickel electrode composition and a preparation method and application thereof.
Background
The chip multilayer ceramic capacitor (MLCC) comprises ceramic dielectric layers and internal electrodes, wherein the internal electrodes are generally obtained by printing internal electrode slurry between two ceramic dielectric layers and then co-firing the internal electrode slurry and the ceramic dielectric layers. In the MLCC product, base metals such as Ni, Cu and the like are mainly used as internal electrode materials, the melting point of the internal electrode materials is low, and the edge parts of the printed patterns of the internal electrodes are easily oxidized in the sintering process, so that the conductivity of the electrode materials is reduced, and the loss is high. At present, a silver-coated nickel material is generally adopted as a powder material of the electronic paste, so that the oxidation resistance of the MLCC electrode material is improved, but the method for preparing the electronic powder has high cost and certain pollution, and the preparation process is not easy to control; and when a high-capacity and multi-layer MLCC product is prepared, the Ni electrode accounts for more, the sintering shrinkage difference between the Ni electrode and a dielectric layer is larger, the interlayer bonding force is reduced, the accumulated stress is increased, the bonding force is poorer, the delamination and cracking are more easily caused, and the like. At present, most manufacturers do not sufficiently research the microscopic mechanism of the MLCC product spalling, and the problem of the MLCC product spalling cannot be fundamentally solved.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a nickel electrode composition which can prevent Ni from being oxidized in a sintering process and is not easy to generate spalling.
Meanwhile, the invention also provides a preparation method and application of the nickel electrode composition.
Specifically, in order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a nickel electrode composition, which is prepared from the following raw materials: the nickel electrode composition comprises nickel, ceramic and non-nickel metal, wherein the mass percentage of the non-nickel metal in the nickel electrode composition is 1% -3%.
The nickel electrode composition according to the first aspect of the invention has at least the following advantageous effects:
the nickel electrode composition is used as an inner electrode slurry of a ceramic capacitor, other metals with specific content are added on the basis of nickel powder, in the co-sintering process of the nickel electrode composition and a ceramic dielectric layer, the added non-nickel metal is more easily combined with oxygen under the weak oxidation condition, and a Ni-M-O (M represents non-nickel metal) crystalline phase structure is generated on the interface of Ni and the ceramic, so that the oxidation of Ni in the sintering process is prevented, and a secondary phase with stronger bonding force is formed on the interface of Ni and the ceramic, and the secondary phase effectively increases the bonding force between the Ni electrode and the dielectric layer, so that the interlaminar bonding force of I-type MLCC products can be obviously improved, the product delamination risk is reduced, and particularly the products with high capacity and multiple layers are obtained. Meanwhile, if the mass ratio of the non-nickel metal in the MLCC is less than 1 wt%, an obvious effective secondary phase cannot be generated after the MLCC product is co-fired, and the effect of enhancing interlayer bonding force cannot be achieved; if the mass ratio of the non-nickel metal is more than 3 wt%, too many secondary phases are generated in the nickel electrode, resulting in aggregation of the secondary phases, causing deterioration in spatial continuity of the nickel electrode and deterioration in electrical properties of the product.
In some embodiments of the invention, the non-nickel metal comprises any one or more of manganese, magnesium, aluminum, vanadium, cobalt, rare earth metals. Non-nickel metals are selected for metal elements that readily react with oxygen to form secondary phases, as well as for multivalent, variable-valence metals, while base metals that are relatively inexpensive are preferred.
In some embodiments of the present invention, the raw material for preparing the nickel electrode composition further comprises any one or more of a binder, an adhesion promoter, a solvent and a dispersant, and preferably comprises the combination of the binder, the adhesion promoter, the solvent and the dispersant.
In some embodiments of the present invention, the nickel electrode composition comprises the following raw materials by mass percent:
45 to 50 percent of nickel
10 to 15 percent of ceramic
1 to 3 percent of non-nickel metal
2 to 3 percent of adhesive
1 to 3 percent of tackifier
30 to 35 percent of solvent
1 to 2 percent of dispersant.
In some embodiments of the present invention, the nickel electrode composition comprises the following raw materials by mass percent:
45 to 50 percent of nickel
10 to 15 percent of ceramic
1.5 to 2.5 percent of non-nickel metal
2 to 3 percent of adhesive
1 to 3 percent of tackifier
30 to 35 percent of solvent
1 to 2 percent of dispersant.
In some embodiments of the invention, the nickel, ceramic and non-nickel metal are in the form of a slurry or powder, preferably a powder.
In some embodiments of the present invention, the ceramic comprises any one or more of a class I ceramic dielectric material such as calcium zirconate, strontium zirconate, calcium zirconate titanate, calcium strontium zirconate titanate, and the like.
In some embodiments of the invention, the binder comprises any one or more of ethyl cellulose resin, nitrocellulose, polyisoethylene, BM-SZ (polyvinyl butyral resin).
In some embodiments of the invention, the tackifier comprises any one or more of tributyl citrate, dioctyl phthalate, rosin, acrylic resin, dibutyl phthalate.
In some embodiments of the invention, the solvent comprises any one or more of terpineol, octanol, dihydroterpineol acetate, ethylene glycol dibutyl ether, polyethylene glycol monomethyl ether acetate, polyethylene glycol monobutyl ether acetate.
In some embodiments of the invention, the dispersant comprises one or more of BKY-410, BYK-420, BYK-405, BYK-411, BYK-428, BYK-430, or BYK-431 from Bick.
The second aspect of the present invention provides a method for preparing the above nickel electrode composition, comprising the steps of: and mixing the preparation raw materials of the nickel electrode composition to obtain the nickel electrode composition.
More specifically, the preparation method of the nickel electrode composition comprises the following steps:
dispersing a dispersing agent and a tackifier in a part of solvent, adding nickel for mixing, adding an adhesive dissolved in the rest solvent, and dispersing until the system is free from agglomeration;
adding ceramic and non-nickel metal, dispersing until the system is free from agglomeration to obtain the nickel electrode composition.
In some embodiments of the invention, the method of making the nickel electrode composition comprises the steps of:
1) dissolving the adhesive by using a part of solvent, and adjusting the mass concentration of the adhesive to 8-10%;
2) mixing a dispersing agent, a tackifier and the residual solvent, adding nickel powder, uniformly stirring, grinding and dispersing for 6-8 times by a three-roll mill at 200-600 rpm, adding the binder dissolved in the step 1), uniformly stirring, grinding and dispersing for 2-4 times by the three-roll mill at 200-600 rpm, and dispersing until no agglomeration exists;
3) weighing ceramic powder and non-nickel metal powder, uniformly mixing the ceramic powder and the non-nickel metal powder with the slurry obtained in the step 2), uniformly stirring, grinding and dispersing for 6-8 times by a three-roll mill at 200-600 rpm until no agglomeration exists;
4) centrifuging and filtering the slurry obtained in the step 3) by using a centrifugal machine to obtain the nickel electrode composition.
A third aspect of the present invention is to provide an internal capacitor electrode obtained by sintering the above nickel electrode composition.
In some embodiments of the present invention, the sintering temperature is 1150-1300 ℃, the oxygen potential for sintering is 600-800 mV, and the sintering time is 30-160 min.
The invention also provides a ceramic capacitor, which contains the capacitor internal electrode.
In some embodiments of the present invention, the ceramic capacitor is a chip multilayer ceramic capacitor (MLCC).
Compared with the prior art, the invention has the following beneficial effects:
the nickel electrode composition of the invention takes metallic nickel powder as a main material, takes ceramic powder as a co-material, and prepares the internal electrode slurry capable of being co-fired with the ceramic material in a weak oxidation atmosphere after adding non-nickel metal powder such as Mn, Mg, Al and the like and dispersing uniformly, and the chip multilayer ceramic capacitor prepared by adopting the internal electrode slurry. The nickel electrode slurry and the ceramic dielectric layer need to be co-fired in the preparation process of the ceramic capacitor. In the co-firing process of the nickel electrode slurry and the ceramic dielectric layer, the added non-nickel metal powder phase such as Mn, Mg, Al and the like is easier to combine with oxygen under a weak oxidation condition than Ni, and crystalline phase structures of Ni-Mn-O, Ni-Mg-O and Ni-Al-O are generated on the interface between Ni and the ceramic, so that on one hand, the oxidation of Ni in the sintering process is prevented, and on the other hand, a secondary phase with stronger bonding force is formed on the interface between Ni and the ceramic, the secondary phase effectively increases the bonding force between the Ni electrode and the dielectric layer, can obviously improve the interlayer bonding force of I-type MLCC products, and reduces the product spalling risk, especially high-capacity and multi-layer products.
Drawings
FIG. 1 shows the results of the Vickers indentation test of the surface of an internal electrode obtained by sintering the nickel electrode paste of example 1;
FIG. 2 shows the results of the Vickers indentation test of the surface of the internal electrode obtained by sintering the nickel electrode paste of comparative example 2;
FIG. 3 shows EPMA test results of the internal electrode surface obtained by sintering the nickel electrode slurry of comparative example 2;
FIG. 4 shows the EPMA test results of the internal electrode surface obtained by sintering the nickel electrode slurry of example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
A nickel electrode slurry for MLCC is prepared from the raw materials shown in Table 1, and the preparation method comprises the following steps:
1) firstly, dissolving the adhesive by using a part of solvent for later use, and adjusting the mass concentration of the adhesive to 10%;
2) mixing the residual solvent, the dispersant and the tackifier, adding nickel powder with uniform particle size distribution after uniformly stirring, continuously stirring for 30min, grinding and dispersing for 6-8 times by using a three-roll mill at 500rpm, adding the binder dissolved in the step 1), uniformly stirring, grinding and dispersing for 2-4 times by using a three-roll mill at 350rpm, and dispersing until no agglomeration exists;
3) weighing ceramic powder and non-nickel metal powder, mixing the ceramic powder and the non-nickel metal powder with the slurry obtained in the step 2), uniformly stirring, and then grinding and dispersing for 6-8 times at 550rpm of a three-roll mill until no agglomeration exists;
4) step 3), after the slurry is uniformly dispersed, centrifuging and filtering by using a centrifuge; filtering to obtain the nickel electrode slurry.
TABLE 1 preparation of Nickel electrode slurries
The performance of the nickel electrode slurry is tested by the following method:
(1) viscosity of the oil
The nickel electrode slurry was measured at room temperature using a 4# pin of a DV-I + viscometer at 10 rpm.
(2) Particle size
A certain amount of nickel electrode slurry, about 2g, was taken and the particle size was measured using a particle size analyzer.
(3) Degree of dispersion
a. Taking the finished slurry after viscosity adjustment and filtration on a glass plate, and scraping the finished slurry into a piece of uniformly distributed slurry by using a gap with the thickness of 200 mu m of a coater;
b. drying the glass plate in an oven at 110 ℃ for 5-10 min;
c. and measuring the surface roughness of the slurry by using a 3D laser microscope, taking 10 pictures under a 1000-time lens, and uniformly dispersing if no agglomeration exists.
(4) Capacity (Cp) and loss (Df)
Printing nickel electrode slurry between ceramic dielectric layers, sintering to form an inner electrode (the sintering temperature is about 1200 ℃, the oxygen potential is about 700mV, and the heat preservation time at 1200 ℃ is about 100min), preparing a multilayer ceramic capacitor product, and setting the voltage to 1V and the test frequency to 1KHZ by using a capacitance meter (KEYSIGHT model E4981A), and testing the capacity (Cp) and the loss (Df) at the room temperature of 25 ℃.
(5) SAT test
And printing nickel electrode slurry between the ceramic medium layers, sintering to form an inner electrode, manufacturing a multilayer ceramic capacitor product, scanning by using an ultrasonic imager and an SK120/CP type probe, and counting the SAT fraction defective of the product.
The test results are shown in table 2 below.
TABLE 2 Nickel electrode paste Performance test results
The detection results of the examples 1 to 5 and the comparative examples 1 and 2 show that the addition of non-nickel metal powder such as Mn, Mg, Al and the like in the process of preparing the nickel electrode slurry has no influence on the conventional performances such as viscosity, granularity, roughness and the like of the nickel electrode slurry. As can be seen from the examples 1 and the comparative examples 2, the addition of too little or no metal powder can not generate the crystalline phase structure of Ni-Mn-O or Ni-Mg-O, Ni-Al-O on the interface of the ceramic dielectric layer and the inner electrode layer, and the crystalline phase structure can not play a role in enhancing the interlayer bonding force, so the interlayer bonding force of the product is poor, the defects such as cracks and the like are easy to occur, and the SAT fraction defective is high; it can be seen from example 4 and comparative example 1 that, when the amount of the non-nickel metal powder is too much, too many secondary phases are generated in the nickel electrode, which causes aggregation of the secondary phases, resulting in poor spatial continuity of the nickel electrode, and poor electrical properties of the product, the product capacity is relatively low, and the use requirement cannot be met.
Internal stress analysis (load force: 25 to 100gf, dwell time: 10 to 20s) was performed on the internal electrodes obtained by sintering the nickel electrode pastes of example 1 and comparative example 2 using a vickers hardness tester, and indentation and vicinity were observed using SEM, and the results are shown in fig. 1 and 2. SEM observation of example 1 with no or very little cracking at the electrode near the indentation; the SEM observation showed that there was a significant crack at the electrode near the indentation in comparative example 2, and the crack length was significantly longer than in the sample of FIG. 1. The sample of comparative example 2 has a very weak bonding force with the ceramic interface, and when vickers indentation is performed near the inner electrode, cracks are clearly seen at the interface between the inner electrode and the ceramic and propagate along the Ni electrode.
Through EPMA test of a cracked sample and a non-cracked sample, components near the inner electrode are analyzed, and the result shows that Ni-Mn-O exists near the inner electrode of the non-cracked sample in the embodiment 1, which shows that the Ni-Mn-O phase existing at the interface of the inner electrode layer and the dielectric layer can increase the interface bonding force, so that the bonding between the inner electrode layer and the dielectric layer of the class I MLCC product is firmer, cracks are less prone to generate, and the interlayer cracking problem of the class I MLCC product can be effectively inhibited; in contrast, in comparative example 2, due to the excessively low Mn content, an obviously effective secondary phase cannot be generated after the MLCC product is co-fired, and the interlayer bonding force cannot be enhanced. Specific detection results are shown in fig. 3 and 4 below.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A nickel electrode composition characterized by: the nickel electrode slurry is prepared from the following raw materials: the nickel electrode composition comprises nickel, ceramic and non-nickel metal, wherein the mass percentage of the non-nickel metal in the nickel electrode composition is 1% -3%.
2. The nickel electrode composition of claim 1, wherein: the non-nickel metal comprises any one or more of manganese, magnesium, aluminum, vanadium, cobalt and rare earth metal.
3. The nickel electrode composition of claim 1, wherein: the raw materials for preparing the nickel electrode composition also comprise any one or more of a combination of a bonding agent, a tackifier, a solvent and a dispersing agent; preferably comprising a combination of adhesives, tackifiers, solvents, dispersants.
4. The nickel electrode composition of claim 3, wherein: the nickel electrode composition comprises the following preparation raw materials in percentage by mass:
45 to 50 percent of nickel
10 to 15 percent of ceramic
1 to 3 percent of non-nickel metal
2 to 3 percent of adhesive
1 to 3 percent of tackifier
30 to 35 percent of solvent
1 to 2 percent of dispersant.
5. The nickel electrode composition of claim 4, wherein: the nickel electrode composition comprises the following preparation raw materials in percentage by mass:
45 to 50 percent of nickel
10 to 15 percent of ceramic
1.5 to 2.5 percent of non-nickel metal
2 to 3 percent of adhesive
1 to 3 percent of tackifier
30 to 35 percent of solvent
1 to 2 percent of dispersant.
6. The nickel electrode composition according to any one of claims 1 to 5, wherein: the ceramic comprises any one or more of calcium zirconate, strontium zirconate, calcium zirconate titanate and strontium calcium zirconate titanate.
7. A method for producing the nickel electrode composition according to any one of claims 1 to 6, characterized in that: the method comprises the following steps: and mixing the preparation raw materials of the nickel electrode composition to obtain the nickel electrode composition.
8. The method according to claim 7, wherein: the preparation method of the nickel electrode composition comprises the following steps:
dispersing a dispersing agent and a tackifier in a part of solvent, adding nickel for mixing, adding an adhesive dissolved in the rest solvent, and dispersing until the system is free from agglomeration;
adding ceramic and non-nickel metal, dispersing until the system is free from agglomeration to obtain the nickel electrode composition.
9. An internal electrode for a capacitor, comprising: the capacitor internal electrode is obtained by sintering the nickel electrode composition according to any one of claims 1 to 6.
10. A ceramic capacitor, characterized by: the ceramic capacitor comprising the capacitor internal electrode according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110583542.6A CN113410050B (en) | 2021-05-27 | 2021-05-27 | Nickel electrode composition and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110583542.6A CN113410050B (en) | 2021-05-27 | 2021-05-27 | Nickel electrode composition and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113410050A true CN113410050A (en) | 2021-09-17 |
| CN113410050B CN113410050B (en) | 2022-07-22 |
Family
ID=77674604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110583542.6A Active CN113410050B (en) | 2021-05-27 | 2021-05-27 | Nickel electrode composition and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113410050B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114709006A (en) * | 2022-04-26 | 2022-07-05 | 深圳市基克纳科技有限公司 | Nickel-chromium electrothermal slurry and preparation method and application thereof |
| CN117542655A (en) * | 2023-12-08 | 2024-02-09 | 南充三环电子有限公司 | Multilayer chip ceramic capacitor and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307941A (en) * | 2000-04-21 | 2001-11-02 | Shoei Chem Ind Co | Terminal electrode paste and method for manufacturing laminated ceramic capacitor |
| US20020149901A1 (en) * | 2000-12-28 | 2002-10-17 | Hitoshi Shindo | Laminate-type dielectric device, a production method and an electrode paste material |
| CN1832068A (en) * | 2006-03-10 | 2006-09-13 | 潮州三环（集团）股份有限公司 | Inner electrode size of ceramic capacitor and preparation method thereof |
| US20110157768A1 (en) * | 2009-12-30 | 2011-06-30 | Samsung Electro-Mechanics Co., Ltd. | Multilayer ceramic capacitor and method of manufacturing the same |
| CN104576043A (en) * | 2014-11-07 | 2015-04-29 | 广东风华高新科技股份有限公司 | Inner electrode paste |
| US20160358713A1 (en) * | 2015-06-05 | 2016-12-08 | Murata Manufacturing Co., Ltd. | Multilayer ceramic capacitor and method for producing the same |
| CN112768234A (en) * | 2020-12-28 | 2021-05-07 | 潮州三环（集团）股份有限公司 | Nickel electrode slurry and preparation method and application thereof |
-
2021
- 2021-05-27 CN CN202110583542.6A patent/CN113410050B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307941A (en) * | 2000-04-21 | 2001-11-02 | Shoei Chem Ind Co | Terminal electrode paste and method for manufacturing laminated ceramic capacitor |
| US20020149901A1 (en) * | 2000-12-28 | 2002-10-17 | Hitoshi Shindo | Laminate-type dielectric device, a production method and an electrode paste material |
| CN1832068A (en) * | 2006-03-10 | 2006-09-13 | 潮州三环（集团）股份有限公司 | Inner electrode size of ceramic capacitor and preparation method thereof |
| US20110157768A1 (en) * | 2009-12-30 | 2011-06-30 | Samsung Electro-Mechanics Co., Ltd. | Multilayer ceramic capacitor and method of manufacturing the same |
| CN104576043A (en) * | 2014-11-07 | 2015-04-29 | 广东风华高新科技股份有限公司 | Inner electrode paste |
| US20160358713A1 (en) * | 2015-06-05 | 2016-12-08 | Murata Manufacturing Co., Ltd. | Multilayer ceramic capacitor and method for producing the same |
| CN112768234A (en) * | 2020-12-28 | 2021-05-07 | 潮州三环（集团）股份有限公司 | Nickel electrode slurry and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114709006A (en) * | 2022-04-26 | 2022-07-05 | 深圳市基克纳科技有限公司 | Nickel-chromium electrothermal slurry and preparation method and application thereof |
| CN114709006B (en) * | 2022-04-26 | 2024-01-05 | 深圳市基克纳科技有限公司 | Nickel-chromium electric heating slurry and preparation method and application thereof |
| CN117542655A (en) * | 2023-12-08 | 2024-02-09 | 南充三环电子有限公司 | Multilayer chip ceramic capacitor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113410050B (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113410050B (en) | Nickel electrode composition and preparation method and application thereof | |
| JP5569747B2 (en) | Gravure printing conductive paste used for multilayer ceramic capacitor internal electrode | |
| JP2012174797A5 (en) | ||
| JP5262445B2 (en) | Conductive paste for multilayer ceramic capacitor internal electrode | |
| JP2016033998A (en) | Paste for multilayer ceramic capacitor internal electrode, and multilayer ceramic capacitor | |
| US6989110B2 (en) | Electroconductive paste and method of producing the same | |
| JP2013016803A (en) | Conductive paste for internal electrode of multilayer ceramic electronic component and multilayer ceramic electronic component fabricated by including the same | |
| JP3918569B2 (en) | Conductive paste and multilayer ceramic electronic components | |
| CN113168930B (en) | conductive paste | |
| TWI819190B (en) | Conductive paste, electronic components, and laminated ceramic capacitors | |
| JP2002110444A (en) | Conductive paste and laminated ceramic electronic part | |
| CN1598982A (en) | Inner electrode size and ceramic capacitor made by the size | |
| JP2009266716A (en) | Conductive paste, and manufacturing method of laminated ceramic capacitor | |
| JP2015161536A (en) | Evaluation method for coarse particle in conductive powder included in conductive paste | |
| JPH10214520A (en) | Conductive paste | |
| CN113178327A (en) | MLCC copper-clad nickel alloy inner electrode slurry and application thereof | |
| JP6601265B2 (en) | Method for producing conductive paste and method for producing multilayer ceramic capacitor | |
| JP6809280B2 (en) | Method of manufacturing conductive paste | |
| JP2006190491A (en) | Conductive paste for ceramic electronic components and ceramic electronic components | |
| JP7059636B2 (en) | A conductive paste, a dry film thereof, an internal electrode formed by firing the dry film, and a laminated ceramic capacitor having the internal electrode. | |
| JP2003124052A (en) | Conductive paste and laminated ceramic electronic part | |
| JP6844299B2 (en) | Method of manufacturing conductive paste | |
| WO2024010075A1 (en) | Conductive paste, dried film, internal electrode and layered ceramic capacitor | |
| JP4432895B2 (en) | Conductive paste, multilayer ceramic electronic component and manufacturing method thereof | |
| JP4442264B2 (en) | Conductive paste for internal electrodes and multilayer ceramic electronic components |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |