JPH10163066A - Terminal electrode paste, layered ceramic capacitor and manufacturing thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a terminal electrode paste suited to low-equivalent series resistance layered ceramic capacitor by mixing and dispersing an Ni powder or Ni and another metal mixed powder with a vehicle composed of an org. binder and solvent. SOLUTION: A Y oxide powder 15-80vol.% is mixed with an Ni powder, ethylene cellulose 7.5wt.% is dissolved in a solvent contg. terpineol and aromatic naphtha at a wt. ratio of 2:1 to prepare a vehicle which is then added to the mixed powder, kneaded and dispersed to produce a terminal electrode paste. Using a reduction-resistive dielectric powder contg. Ba titanate as a main component, a green chip composed of alternately laminated Ni inner electrodes 1 and dielectric ceramics 2 is formed and chamfered. Using the terminal electrode paste, terminal electrodes 3 are formed, and terminal electrodes 4 are formed, using an Ag paste and a Ni plating layer 5 and solder plating layer 6 are formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a terminal electrode paste for manufacturing terminal electrodes of a multilayer electronic component requiring electrical connection, a multilayer ceramic capacitor using the same, and a method of manufacturing the multilayer ceramic capacitor. is there.

[0002]

2. Description of the Related Art In a multilayer ceramic capacitor, dielectric layers and internal electrode layers are alternately arranged, and dielectric layers for adjusting the overall dimensions and hermetically sealing the inside are provided above and below the laminated structure. The electrical connection of the internal electrode layers is performed by providing terminal electrodes on the two surfaces with their terminal portions exposed. A structure is known in which nickel plating and tin-lead-based solder plating are applied in layers on the surface of these terminal electrodes so that solder mounting can be performed easily and without any trouble.

[0003] In recent years, multilayer ceramic capacitors have been required to have a small size and a large capacity in order to respond to miniaturization of electronic devices. Is being promoted. One of the major issues associated with the high stacking of thin layers is the cost of raw materials for the metal used for the internal electrodes. As a method for solving this problem, it is known to use inexpensive nickel instead of the noble metal such as palladium, which has been conventionally used, and the ratio of nickel internal electrode products in the multilayer ceramic capacitor is rapidly increasing.

Since nickel is a base metal, it cannot be fired in an oxygen atmosphere as in a conventional multilayer ceramic capacitor having a noble metal internal electrode, and must be fired in a low oxygen partial pressure atmosphere so that nickel is not oxidized. Must. A perovskite oxide typified by barium titanate, which is known for capacitors, has a temperature of 1000 ° C.
When exposed to an atmosphere at or below the equilibrium oxygen partial pressure of nickel at the above-mentioned high temperature, it is reduced, the insulation resistance value is reduced, and the function as a dielectric for a capacitor cannot be achieved.

On the other hand, these perovskite oxides
The above-described heat treatment is performed by changing the stoichiometric ratio of ions existing at the site and the B site, or by adding a transition metal ion or the like which can form a solid solution as a donor in the crystal lattice. It is known that reduction is difficult even if the reaction is performed. Nickel internal electrode multilayer ceramic capacitors are made possible by reduction-resistant dielectric materials developed using this property.

Conventionally, a nickel internal electrode multilayer ceramic capacitor is manufactured as follows. The above-mentioned reduction-resistant dielectric material powder was slurried, applied to a substrate, dried to form a green sheet, and a nickel paste was printed on the green sheet to form internal electrodes. Lamination and crimping are performed according to the number of sheets. At this time, only the same green sheets are pressed on the upper and lower portions of the laminate to form a protective layer.

[0007] Next, the laminate is cut into pieces and separated into individual pieces to form raw chips, which are chamfered, and then a first terminal electrode paste containing nickel powder as a main component is applied to the surface where the internal electrode ends are exposed. Apply. These raw chips are debindered, fired in a low oxygen partial pressure atmosphere, and further coated with a second terminal electrode containing silver or a powder of silver and palladium or copper, and a glass frit as main components. After baking, nickel plating and solder plating are sequentially performed.

[0008] The first terminal electrode paste is used to improve the adhesion between the capacitor body and the terminal electrode.
For example, as disclosed in Japanese Patent Application Laid-Open No. 63-86414, a material mainly containing nickel powder and the same ceramic powder as a dielectric material constituting a multilayer capacitor is used.

[0009]

As described above, since the nickel internal electrode multilayer ceramic capacitor is manufactured by firing in a reducing atmosphere, fine adjustment of the A site / B site ratio and effective addition of additives are required. The use of a doped dielectric composition having reduced resistance is still inferior in reliability to a multilayer ceramic capacitor manufactured in an oxygen atmosphere such as air.

It is known that nickel causes migration when an electric field is applied in the presence of moisture,
In the case of a multilayer ceramic capacitor, there is a problem that after a long time, the insulation resistance is reduced, and furthermore, a short circuit is caused. These phenomena appear as defects such as a decrease in insulation resistance in a heat resistance load life test and a moisture resistance load life test of a nickel internal electrode multilayer ceramic capacitor.

In order to prevent this and to assure reliability, a material composed of nickel powder and a dielectric powder constituting the capacitor is provided on the surface where the terminal ends of the internal electrodes are exposed, as described above, to prevent intrusion of moisture and the like. Cut off. However, in order to sufficiently obtain this effect, it is necessary to increase the proportion of the dielectric powder to increase the adhesion of the first terminal electrode to the capacitor body. However, in such a composite of a metal and a dielectric, the volume resistivity is increased, the equivalent series resistance of the manufactured multilayer ceramic capacitor is essentially increased, and the manufacturing yield due to variations in capacitance and dielectric loss is increased. There is a problem that causes a decrease in

The present invention solves the above-mentioned problems and provides a terminal electrode paste capable of realizing a multilayer ceramic capacitor having a low equivalent series resistance value and excellent in durability reliability, a multilayer ceramic capacitor using the same, and,
It is an object of the present invention to provide a method for manufacturing the multilayer ceramic capacitor with good yield.

[0013]

In order to solve the above problems, a terminal electrode paste according to the present invention comprises nickel powder,
Or a mixed powder of nickel and another metal,
It is obtained by mixing and dispersing a powder obtained by mixing a volume% of oxide powder and a vehicle comprising an organic binder and a solvent.

When the terminal electrode paste is used as the terminal electrode of the multilayer ceramic capacitor by including the oxide at the above content, the exposed surface of the internal electrode terminal portion is completely shut off from the outside world, The volume resistivity of the object becomes extremely low. Therefore, it is possible to configure a terminal electrode that fully maintains the characteristics as a conductor while completely ensuring the airtightness of the multilayer ceramic capacitor. As a result, the durability reliability is improved, the equivalent series resistance value of the multilayer ceramic capacitor is reduced, and variations in capacitance and dielectric loss are eliminated.

The oxide powder is mainly composed of a titanate of an alkaline earth metal, and contains 0.1 to 5.0 mol% of Y, La, Pr, Ce, Nd, Eu, Gd, Tb, Db.
It is preferable to mix at least one metal oxide selected from y, Ho, Er, Tm, Yb and Lu.

Next, a multilayer ceramic capacitor according to the present invention is a multilayer ceramic capacitor comprising a barium titanate-based ceramic powder imparted with reduction resistance and a nickel internal electrode, formed from any one of the terminal electrode pastes described above. Terminal electrodes.

Since the terminal electrode paste as described above is used as the terminal electrode of the multilayer ceramic capacitor, the exposed surface of the terminal portion of the internal electrode is completely cut off from the outside, and the volume resistivity of this oxide becomes extremely low. Therefore,
It is possible to configure a terminal electrode that fully maintains the characteristics as a conductor while completely ensuring the airtightness of the multilayer ceramic capacitor. As a result, the durability reliability is improved, the equivalent series resistance value of the multilayer ceramic capacitor is reduced, and variations in capacitance and dielectric loss are eliminated.

Next, a method of manufacturing a multilayer ceramic capacitor according to the present invention is a method of manufacturing a multilayer ceramic capacitor including a barium titanate-based ceramic powder having reduced resistance and a nickel internal electrode. A step of applying any one of the above terminal electrode pastes as a first terminal electrode to the internal electrode extraction surface of the raw chip of the capacitor, a step of chamfering the raw chip coated with the terminal electrode paste, A step of firing the chip in a reducing atmosphere in which nickel is not oxidized after removing the binder, a step of applying and firing a second terminal electrode on the fired chip, and a step of plating nickel and soldering on the second terminal electrode. The step of sequentially applying plating is performed sequentially.

Next, another method of manufacturing a multilayer ceramic capacitor according to the present invention is a method of manufacturing a multilayer ceramic capacitor including a barium titanate-based ceramic powder provided with reduction resistance and a nickel internal electrode. A step of chamfering the raw chip of the multilayer ceramic capacitor, a step of applying any one of the terminal electrode pastes as a first terminal electrode to the internal electrode extraction surface of the chamfered raw chip, and a step of applying the terminal electrode paste. Removing the burned chip after debinding, firing in a reducing atmosphere in which nickel is not oxidized;
And a step of sequentially applying nickel plating and solder plating on the second terminal electrode.

Next, still another method of manufacturing a multilayer ceramic capacitor according to the present invention is a method of manufacturing a multilayer ceramic capacitor including a barium titanate-based ceramic powder provided with reduction resistance and a nickel internal electrode. A step of applying any one of the above terminal electrode pastes as a first terminal electrode to the internal electrode extraction surface of the raw chip of the multilayer ceramic capacitor, and removing the raw chip to which the terminal electrode paste has been applied by removing nickel. Baking in a reducing atmosphere in which is not oxidized; chamfering the fired chip; applying and baking a second terminal electrode to the chamfered chip; and forming nickel on the second terminal electrode. The step of sequentially performing plating and solder plating is performed sequentially.

In each of the above-described methods for manufacturing a multilayer ceramic capacitor, a terminal electrode paste is applied to an exposed surface of an internal electrode terminal portion of a raw chip or a chamfered raw chip, and the multilayer ceramic capacitor raw chip and the terminal electrode paste are simultaneously fired. By doing so, it is possible to form a terminal electrode that fully maintains the characteristics as a conductor while completely ensuring the airtightness of the multilayer ceramic capacitor. As a result,
The durability reliability is improved, the equivalent series resistance value of the multilayer ceramic capacitor is reduced, and there is no variation in capacitance and dielectric loss, so that the production yield of the multilayer ceramic capacitor can be improved.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described. (Embodiment 1) 100 g of barium titanate powder (manufactured by Nippon Kagaku Sangyo Co., Ltd., BTG-L) is mixed with yttrium oxide (Yttrium Japan Co., Ltd.) in the amount shown in Table 1.
Made of pure water as a ball mill (using 0.5 liter, 5 mmφ zirconia balls as spheres)
And wet mixed. Various mixing conditions were examined, but it was sufficient that the rotation speed was 100 times / min for about 15 hours, and the characteristics obtained finally did not change even if more time was applied. After drying this mixed powder, the temperature is raised in air from normal temperature at 200 ° C./hour, and kept at 1100 ° C. for 2 hours.
Heat treatment with a heat treatment profile of temperature reduction at ℃, and after performing ball mill pulverization under the same conditions as when mixing, dried
An oxide powder was prepared.

These oxide powders are press-molded into a disk having a diameter of 12 mm and a thickness of about 0.7 mm, and are heated at a temperature of from room temperature to 900 ° C. per hour in a mixed gas atmosphere of nitrogen and hydrogen.
The temperature was raised at 0 ° C., and while maintaining the temperature at 900 ° C. for 1 hour, the mass flow controller was operated to adjust the oxygen partial pressure so as to be two orders of magnitude lower than the redox equilibrium oxygen partial pressure of nickel.
After that, while operating the mass flow controller so that the oxygen partial pressure is maintained at each temperature, the temperature is raised at 200 ° C./hour to 1300 ° C., and the temperature is maintained at 1300 ° C. for 2 hours.
Firing was performed at a temperature of 200 ° C./hour to room temperature. Gold was vacuum-deposited on the front and back surfaces of these sintered disks to form electrodes, and the volume resistivity was measured. In addition,
At this time, a sintered disk was similarly prepared for the mixed powder that had not been subjected to the above-described heat treatment in the atmosphere, and the measurement was performed.
Table 1 shows the results.

[0024]

[Table 1]

As is clear from Table 1, it is found that a barium titanate doped with 0.1 mol% or more of yttrium oxide gives a low-resistance sintered body by firing in a reducing atmosphere. However, when the yttrium oxide content exceeds 5.0 mol%, 1300
At ℃, sintering stops. For these compositions,
Sintering was attempted by raising the temperature to 350 ° C., but was impossible. Also, as can be seen from Table 1, 1100
Comparing the case where the heat treatment was performed at ℃ and the case where the heat treatment was not performed, no significant difference was observed between the two.

Nickel powder (manufactured by Sumitomo Metal Mining, SNP-
130) 50 g of the oxide powder No. 1 in Table 1. 10 and powder having the composition shown in Table 2 and then mixed with terpineol and aromatic naphtha at a ratio of 2: 1 by weight to a solvent obtained by mixing ethyl cellulose (Ethocel 45, manufactured by Dow Chemical Co., Ltd.).
Was added so that ethyl cellulose was 5% by weight with respect to the total amount of the above-mentioned mixed powder.

After the preliminary kneading, the mixture was kneaded and dispersed by a three-roll mill (alumina roll, 50 mmφ) to prepare a terminal electrode paste. Before applying these pastes, the viscosity of the paste is adjusted by adding a solvent having the same composition as that of the vehicle.
At 5 ° C., the pressure was adjusted to 4 to 5 Pa · s.

Next, a method for manufacturing a multilayer ceramic capacitor using the terminal electrode paste prepared as described above will be described. FIG. 1 is a diagram illustrating a method for manufacturing the multilayer ceramic capacitor of the first embodiment.

A reduction-resistant dielectric powder prepared by adding barium titanate as a main component and a small amount of additives such as magnesium oxide, yttrium oxide, manganese oxide and silica to an organic vehicle containing polyvinyl butyral as a main component Using a dielectric slurry dispersed in
A μm green sheet was prepared, and a commercially available nickel paste was printed thereon to form an internal electrode pattern. Only 25 green sheets each as a protective layer above and below,
100 green sheets on which internal electrode patterns were formed were laminated and pressed, and cut into individual pieces to produce 3216 size multilayer capacitor raw chips. As a result, as shown in FIG. 1, a raw chip in which nickel internal electrodes 1 and derivative ceramics 2 were alternately laminated was manufactured.

These raw chips were chamfered by using a zirconia ball as a cobblestone by a ball mill, and the above-mentioned terminal electrode paste was applied as a first terminal electrode 3 to the exposed surface of the internal electrode terminal as shown in FIG. Next, in the atmosphere,
After the temperature was raised to 350 ° C. at 15 ° C./hour, and the temperature was maintained at 350 ° C. for 5 hours, the binder was removed in a profile of cooling in the furnace, and firing was performed in the same manner as the firing profile described above.
As a second terminal electrode 4, a commercially available silver paste was applied to these fired chips as shown in FIG. 1, and baked in air using a belt furnace with a profile of a maximum temperature of 650 ° C. and a processing time of 1 hour. Finally, a nickel plating layer 5 is formed on the surface of the second terminal electrode 4 by electroplating in a plating bath containing an aqueous solution of nickel sulfate and nickel chloride as a main component, and an aqueous borofluoride solution of lead and tin is mainly used. Electroplating was performed in a plating bath as a component to form a solder plating layer 6. Table 2 shows the results of measuring the initial characteristics and the load life reliability of the multilayer ceramic capacitor manufactured as described above.

[0031]

[Table 2]

As a comparative example, a multilayer ceramic capacitor manufactured by applying a terminal electrode paste prepared in exactly the same manner as described above to a raw chip using the reduction-resistant dielectric powder used in the dielectric slurry was also used. Table 3 shows the results of measuring the initial characteristics and the load life reliability.

[0033]

[Table 3]

In Tables 2 and 3, the heat resistance refers to the number of multilayer capacitors whose insulation resistance value has dropped to 100 MΩ or less when a DC voltage of 32 V is applied at 125 ° C. and 1000 hours have passed. Similar numbers are shown when a DC 16 V is applied under a high temperature and high humidity of 85% RH and 1000 hours have passed.
00. These reliability tests were performed with the test sample mounted on a glass epoxy substrate by dipping in a solder bath at 270 ° C. The equivalent series resistance (ESR) is a value measured using an impedance analyzer.

As is clear from these tables, the multilayer ceramic capacitor according to the present invention has a variation in capacitance and dielectric loss as compared with a conventional multilayer ceramic capacitor having terminal electrodes using a reduction-resistant dielectric powder. And the value of the equivalent series resistance is small. However, as shown in the table, when the content of the oxide powder is less than 15% by volume, the airtightness is reduced, so that there is a problem particularly with respect to the moisture resistance load life. When the number is large, the variation between the capacitance and the dielectric loss (tan δ) is slightly increased, and the value of the equivalent series resistance is increased. Therefore, the content of the oxide powder is preferably 15% by volume to 80% by volume.

In the present embodiment, the results in the case of using nickel powder as the metal powder of the terminal electrode paste have been shown. However, the type of metal to be used as the second terminal electrode and the compatibility with the paste are as follows. For example, the same result as in the present embodiment can be obtained by using a mixture of nickel powder with palladium powder, copper powder, cobalt powder, or the like. However, in these cases, the value of the equivalent series resistance changes slightly depending on the intrinsic resistivity of the sintered alloy.

In the case of manufacturing a multilayer ceramic capacitor using a barium titanate-based ceramic powder having reduced resistance as the oxide powder of the terminal electrode paste, the sintering behavior of the multilayer ceramic capacitor is matched. It is preferable that the main component is barium titanate, which is an alkaline earth metal titanate as in the embodiment, and at least one of the oxides according to claim 2 is 0.1 mol.
% To 5.0 mol% are preferable. However, in the case of a laminated electronic component using another alkaline earth metal titanate, for example, a laminated varistor having a nickel internal electrode using strontium titanate as a main component, strontium titanate may be used. it can.

(Embodiment 2) Dysprosium oxide (Dy ₂ O ₃ ) (Shin-Etsu Chemical Co., Ltd.) having the composition shown in Table 4 was added to 100 g of barium titanate powder (HPBT, manufactured by Sakai Chemical Co., Ltd.). , Ball mill using pure water (Capacity:
A zirconia ball having a diameter of 0.5 liter and a diameter of 5 mm is used as a cobblestone. ), And wet-mixed at a rotation speed of 100 times / minute for 15 hours. After drying, crushing was performed to prepare an oxide powder.

Nickel powder (manufactured by Sumitomo Metal Mining, SNP-
700) 50 g of the prepared oxide powder was mixed with 50 g, and polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., B
A vehicle in which 10% by weight of (LS) was dissolved was added so that polyvinyl butyral was 7% by weight based on the total amount of the mixed powder. After the preliminary kneading, the mixture was kneaded and dispersed by a three-roll mill (alumina roll, 50 mmφ) to prepare a terminal electrode paste. Before application, terpineol was added to these pastes to adjust the viscosity, so that the viscosity was 4 to 5 Pa · s at 25 ° C.

Next, a method of manufacturing a multilayer ceramic capacitor using the terminal electrode paste prepared as described above will be described. FIG. 2 is a diagram illustrating a method for manufacturing the multilayer ceramic capacitor of the first embodiment.

A reduction-resistant dielectric powder prepared by adding a small amount of additives such as barium titanate, strontium carbonate, magnesium oxide, dysprosium oxide, manganese oxide, and silica to polyvinyl butyral is used. A green sheet having a thickness of 10 μm was prepared using a dielectric slurry dispersed in an organic vehicle to be used, and a commercially available nickel paste was printed thereon to form an internal electrode pattern. Thirty green sheets alone as upper and lower protective layers were each laminated, and 120 green sheets on which internal electrode patterns were formed were laminated and pressed, and cut into individual pieces to produce 3216 size multilayer capacitor raw chips.

The above-mentioned terminal electrode paste was applied as the first terminal electrode 3 to the exposed surfaces of the internal electrode terminal portions of these raw chips as shown in FIG. Next, the zirconia balls were chamfered with a ball mill using a ball mill, the temperature was raised to 350 ° C. at 15 ° C./hour in the atmosphere, the temperature was maintained at 350 ° C. for 5 hours, and then the binder was removed in a furnace. Was fired in the same manner as in the firing profile. As the second terminal electrode 4, a commercially available copper paste was applied to these fired chips as shown in FIG. 2 and baked in a nitrogen atmosphere using a belt furnace at a maximum temperature of 750 ° C. and a processing time of 1 hour. Finally, a nickel plating layer 5 and a solder plating layer 6 were formed on the second terminal electrode in the same manner as in the first embodiment. Table 4 shows the results of measuring the initial characteristics and the load life reliability of the multilayer ceramic capacitor manufactured as described above.

[0043]

[Table 4]

In Table 4, in terms of heat resistance and moisture resistance, the same numbers as in Tables 2 and 3 of Embodiment 1 are shown. In the case of a terminal electrode paste using an oxide powder containing more than 5 mol% of dysprosium oxide, sintering was insufficient and strength was small, and thus evaluation was not performed. As is clear from this table, the multilayer ceramic capacitor according to the present embodiment has the same excellent characteristics as described in the first embodiment, and the oxides outside the composition range specified by the present embodiment. In the case of a powder, its properties are not exhibited.

After chamfering the multilayer capacitor raw chip coated with the terminal electrode paste according to the present embodiment,
Although the manufacturing method of performing binder removal and firing was shown, as shown in FIG. 3, the laminated capacitor raw chip coated with the terminal electrode paste prepared in the present embodiment was removed from the binder, fired, and then zirconia balls were removed. Using a silicon carbide powder (325 mesh) and chamfering by ball milling using pure water as a medium, a multilayer ceramic capacitor was similarly manufactured and evaluated, and almost the same results as shown in Table 4 were obtained. Was.

As described above, in the first and second embodiments, the metal oxide mixed with the alkaline earth metal titanate according to the dielectric composition of the multilayer ceramic capacitor to be provided with the terminal electrode paste The oxide of yttrium (Y) and dysprosium (Dy) was used as the material. However, in the case where the diffusion of metal ions in the firing process and the deterioration of the dielectric itself due to the reaction become a problem, 0.1 to 5.0 mol is used. % Of La, Pr, Ce, N
Similar effects can be obtained by using any of metal oxides selected from d, Eu, Gd, Tb, Ho, Er, Tm, Yb and Lu. In other words, barium titanate-based ceramics provided with reduction resistance, which constitute a multilayer ceramic capacitor, are formed using various trace additives in order to satisfy required characteristics such as dielectric constant, dielectric loss and temperature characteristics of capacitance. However, this can be dealt with by selecting the above metal oxide according to the composition. In addition, it is preferable to use 95 mol%-99.9 mol% of alkaline earth metal titanates with respect to each of the above metal oxides. Please ).

[0047]

As described above, according to the present invention,
An electrode laminated ceramic capacitor having a low equivalent series resistance and excellent in durability reliability can be manufactured with good yield.

[Brief description of the drawings]

FIG. 1 is a diagram showing a method for manufacturing a multilayer ceramic capacitor according to a first embodiment of the present invention.

FIG. 2 is a diagram showing a method of manufacturing a multilayer ceramic capacitor according to a second embodiment of the present invention.

FIG. 3 is a diagram showing a method for manufacturing another multilayer ceramic capacitor according to the second embodiment of the present invention;

[Explanation of symbols]

 Reference Signs List 1 nickel internal electrode 2 dielectric ceramic 3 first terminal electrode 4 second terminal electrode 5 nickel plating layer 6 solder plating layer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideaki Omura 1006 Kazuma Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.

Claims (6)

[Claims] 1. A mixture comprising nickel powder or a mixed powder of nickel and another metal, and a powder obtained by mixing 15 to 80% by volume of an oxide powder, and a vehicle comprising an organic binder and a solvent, Terminal electrode paste dispersed. 2. The oxide powder contains, as a main component, a titanate of an alkaline earth metal, and contains 0.1 to 5.0 mol% of Y, La, Pr, Ce, Nd, Eu, Gd, Tb, and D.
2. The terminal electrode paste according to claim 1, wherein at least one metal oxide selected from the group consisting of y, Ho, Er, Tm, Yb and Lu is mixed. 3. A multilayer ceramic capacitor comprising a barium titanate-based ceramic powder provided with reduction resistance and a nickel internal electrode, wherein the terminal is formed from the terminal electrode paste according to claim 1 or 2. A multilayer ceramic capacitor comprising an electrode. 4. A method for manufacturing a multilayer ceramic capacitor comprising a barium titanate-based ceramic powder imparted with reduction resistance and a nickel internal electrode, comprising: A step of applying the terminal electrode paste according to claim 1 or 2 as a first terminal electrode, a step of chamfering the raw chip to which the terminal electrode paste is applied, and removing the chamfered raw chip. Thereafter, a step of firing in a reducing atmosphere in which nickel is not oxidized,
A step of applying a second terminal electrode to the fired chip and baking it, and a step of sequentially applying nickel plating and solder plating on the second terminal electrode, sequentially producing a multilayer ceramic capacitor. Method. 5. A method for manufacturing a multilayer ceramic capacitor comprising a barium titanate-based ceramic powder provided with reduction resistance and a nickel internal electrode, comprising: a step of chamfering a raw chip of the multilayer ceramic capacitor; A step of applying the terminal electrode paste according to claim 1 or 2 as a first terminal electrode to the internal electrode extraction surface of the processed raw chip, and removing the raw chip coated with the terminal electrode paste. Thereafter, a step of firing in a reducing atmosphere in which nickel is not oxidized, a step of applying and firing a second terminal electrode on the fired chip, and sequentially applying nickel plating and solder plating on the second terminal electrode And a step of sequentially performing the steps. 6. A method for manufacturing a multilayer ceramic capacitor comprising a barium titanate-based ceramic powder imparted with reduction resistance and a nickel internal electrode, comprising: A step of applying the terminal electrode paste according to claim 1 or 2 as a first terminal electrode, and after removing the raw chip to which the terminal electrode paste has been applied, in a reducing atmosphere in which nickel is not oxidized. Firing step, chamfering the fired chip, applying and baking a second terminal electrode to the chamfered chip, and sequentially applying nickel plating and solder plating on the second terminal electrode Are sequentially performed.