CN113410050A - Nickel electrode composition and preparation method and application thereof - Google Patents
Nickel electrode composition and preparation method and application thereof Download PDFInfo
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- 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
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- 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
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- 239000002184 metal Substances 0.000 claims abstract description 34
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- 238000000034 method Methods 0.000 claims abstract description 14
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- 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
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- 239000010941 cobalt Substances 0.000 claims description 2
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- 150000002910 rare earth metals Chemical class 0.000 claims description 2
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Images
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- 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
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- 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.
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