CN112908697B - Multilayer ceramic capacitor and method for manufacturing same - Google Patents
Multilayer ceramic capacitor and method for manufacturing same Download PDFInfo
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- CN112908697B CN112908697B CN202010244935.XA CN202010244935A CN112908697B CN 112908697 B CN112908697 B CN 112908697B CN 202010244935 A CN202010244935 A CN 202010244935A CN 112908697 B CN112908697 B CN 112908697B
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 212
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- 239000000919 ceramic Substances 0.000 claims abstract description 64
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 60
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
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- 239000003822 epoxy resin Substances 0.000 claims description 6
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- 238000009713 electroplating Methods 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 description 19
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/012—Form of non-self-supporting electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
Abstract
The invention provides a laminated ceramic capacitor and a manufacturing method thereof, wherein the base part of the ceramic capacitor comprises a ceramic dielectric body and a plurality of internal electrodes which are formed in the ceramic dielectric body and are arranged at intervals in a staggered way, two first external electrodes of external electrode layers are sintered at two sides of the base part, the two first external electrodes are electrically contacted with the end parts of the internal electrodes of the plurality of internal electrodes, a second external electrode made of metal powder and resin is formed outside the two first external electrodes, and the internal electrode and the first external electrode are both nickel powder and barium titanate powder with the average grain diameter of 0.2-0.4 mu m, so that the internal electrode and the first external electrode can be well electrically contacted, the mutual bonding strength is improved, and the condition that the first external electrode is stripped from the internal electrode is further reduced, and the electroplating solution is prevented from invading.
Description
Technical Field
The present invention relates to a multilayer ceramic capacitor and a method for manufacturing the same, and more particularly, to a multilayer ceramic capacitor in which an internal electrode and first external electrodes at both sides thereof contain nickel powder and barium titanate powder having an average particle diameter of 0.2 to 0.4 μm, so as to improve electrical contact between the internal electrode and the first external electrodes, improve mutual bonding strength, and reduce peeling.
Background
In terms of function, the Capacitor stores charges in an electrostatic mode, and can release electric energy within a predetermined time, even serving as filtering or bypass for coordinated use; the resistor is used for adjusting the voltage and the current in the circuit; the inductor mainly functions to filter the noise in the current and prevent the electromagnetic interference.
At present, all kinds of information, communication, consumer electronics or other sophisticated electronic products are mutually matched and applied to achieve the purpose of electronic loop control, and because the kind of electronic products has no far-reaching limit, the requirements of the passive components on the capacitor are raised, for example: the capacitor has a smaller size or a higher requirement for dielectric stability, however, the capacitor can be classified into an aluminum electrolytic capacitor, a ceramic capacitor, a plastic film capacitor, a tantalum capacitor, a mica capacitor, etc. according to the material, the ceramic capacitor has the characteristics of high dielectric constant, good insulation, good heat resistance, small volume, suitability for mass production, good stability and reliability, etc., and the ceramic capacitor has the advantages of high voltage and heat resistance and wide operating temperature range, and the ceramic capacitor can be directly welded by a Surface Mount Technology (SMT), so that the production speed and the number of the ceramic capacitor are much better than those of other capacitors such as an electrolytic capacitor, a tantalum capacitor, etc.
Further, ceramic capacitors are widely used, for example: disc-shaped Ceramic capacitors, ingot-shaped Ceramic capacitors, multilayer Ceramic capacitors (MLCC) and the like are typical Ceramic capacitors commonly found in the market, wherein the multilayer Ceramic Capacitor is mainly composed of barium titanate with high dielectric property, the capacitance content of the multilayer Ceramic Capacitor is generally proportional to the surface area of a product and the number of stacked layers of Ceramic films, and the multilayer Ceramic Capacitor is internally formed by alternately stacking an inner electrode Layer, a Ceramic dielectric Layer and an inner electrode Layer in parallel, that is, each Ceramic dielectric Layer is clamped by an upper inner electrode Layer and a lower inner electrode Layer in parallel to form a plate Capacitor, and then is electrically connected with an outer electrode Layer, so that the multilayer Ceramic Capacitor can be used as a container for storing electric quantity.
Furthermore, because of the large number of stacked ceramic dielectric layers and internal electrode layers with staggered intervals, the multilayer ceramic capacitor is the most popular and widely used ceramic capacitor in electronic products, especially in portable high-level electronic and communication products, such as: PC, mobile phone, or automotive electronic component.
In the prior art, as disclosed in japanese patent application laid-open No. 5-3131, a multilayer ceramic capacitor is disclosed, which comprises a multilayer body in which inner electrodes and a ceramic dielectric body are alternately laminated, and outer electrode layers, wherein the inner electrodes of the multilayer ceramic capacitor are made of nickel, and the outer electrode layers at both sides of the ceramic dielectric body include first outer electrodes, second outer electrodes formed by bonding silver (or silver alloy) to the two first outer electrodes through glass, and third outer electrodes formed by plating a metal film on the two second outer electrodes.
The ceramic dielectric body and the first external electrode made of nickel material are arranged around the adjacent combination position, and a diffusion layer of nickel oxide is easily formed due to high sintering temperature, so that the combination strength is improved.
In addition, the second external electrode includes glass powder and silver (or silver alloy) material, so the glass powder is easy to be unevenly distributed, when the glass powder is accumulated around or is densely distributed in a large amount, when the third external electrode is electroplated outside the second external electrode, the electroplating solution (such as nickel electroplating solution) is easy to intrude into the ceramic dielectric body through the diffusion path of the second and first external electrodes, so the compactness of the multilayer ceramic capacitor is seriously poor, the quality is poor, the texture is fragile and easy to crack, and if the multilayer ceramic capacitor is applied to electronic products, the expected normal function of the multilayer ceramic capacitor cannot be exerted, so many defects are needed to be improved.
In addition, the conventional multilayer ceramic capacitor generally uses multiple heating or sintering processes to manufacture the layered structure of the external electrode, but the capacitor is damaged by frequent sintering or excessive heating, especially the internal electrode and the first external electrode, in order to produce the multilayer ceramic capacitor with high capacitance and increase the stacking number of the internal electrodes, many internal electrodes gradually tend to be thinned, so that the contact area between each layer of internal electrode and the first external electrode is reduced, at this time, if the formed first external electrode is affected by the temperature of the subsequent process and the thermal expansion phenomenon occurs, the original contact position between the first external electrode and the internal electrode will be peeled off, even damaged or broken, and the electrical characteristics of the capacitor will be affected.
In addition, the external electrode or the first external electrode of the multilayer ceramic capacitor in the prior art may be made of copper-containing metal or copper metal, but the external electrode and the internal electrode have different thermal expansion coefficients due to different material types, and once the volume of the external electrode and the internal electrode changes due to heating, the original contact position of the first external electrode and the internal electrode is easily damaged.
As described above, the conventional multilayer ceramic capacitor has the above problems, and particularly, the non-uniform presence of glass can cause the plating solution of the external electrode to intrude into the ceramic dielectric during the forming process and cause the reliability cracking, so how to solve the problem of the multilayer ceramic capacitor that the glass powder material or other impurity elements are diffused and intruded is a direction that is urgently desired to be improved by the related manufacturers in the field.
Disclosure of Invention
Therefore, in view of the above-mentioned shortcomings, the present inventors have collected relevant data, evaluated and considered in many ways, and made a trial and modification for years of experience accumulated in the industry, and finally invented the multilayer ceramic capacitor and its manufacturing method.
In order to realize the purpose, the invention adopts the technical scheme that:
a multilayer ceramic capacitor, characterized in that: including the basal portion and the external electrode layer of shaping in the basal portion both sides, wherein:
the base comprises a ceramic dielectric body and a plurality of internal electrodes which are formed in the ceramic dielectric body and are arranged in a staggered and spaced mode, one side edge of each internal electrode is provided with an end part of the internal electrode which is exposed out of the ceramic dielectric body, and the internal electrodes contain nickel powder and barium titanate powder with the average grain diameter of 0.2-0.4 mu m;
the external electrode layer comprises first external electrodes formed on two sides of the ceramic dielectric body of the base part in a sintering way and second external electrodes formed outside the first external electrodes on the two sides, wherein the two first external electrodes are electrically contacted with the end parts of the internal electrodes of the plurality of internal electrodes, the first external electrodes contain nickel powder and barium titanate powder with the average particle size of 0.2-0.4 mu m, and the second external electrodes are formed by metal powder and resin.
The multilayer ceramic capacitor described above, wherein: the base portion and the two first external electrodes of the external electrode layer are sintered by a co-sintering method.
The multilayer ceramic capacitor described above, wherein: the barium titanate powder contained in the internal electrode of the base portion and the first external electrode of the external electrode layer has an average particle diameter of 0.05 to 0.1 [ mu ] m.
The multilayer ceramic capacitor described above, wherein: the volume percentages of barium titanate powder to nickel powder in the internal electrode of the base portion and the first external electrode of the external electrode layer are the same.
The multilayer ceramic capacitor described above, wherein: the volume percentage of barium titanate powder to nickel powder in the first external electrode of the external electrode layer is 15 vol% -50 vol%.
The multilayer ceramic capacitor described above, wherein: the average thickness of the first external electrode is between 5 to 50 μm.
The multilayer ceramic capacitor described above, wherein: the metal powder of the second external electrode is silver powder, silver and nickel mixed powder, copper powder or copper powder with silver coated on the surface, and the resin comprises epoxy resin and thermosetting resin.
A method for manufacturing a multilayer ceramic capacitor, comprising the steps of:
(A) firstly, processing and molding the ceramic slurry into a ceramic thin strip by using a thin strip molding machine;
(B) processing and forming a first nickel electrode paste on the ceramic thin strip to form a nickel electrode paste layer on the ceramic thin strip, and drying the nickel electrode paste layer, wherein the first nickel electrode paste comprises nickel powder and barium titanate powder, and the average particle size of the nickel powder is 0.2-0.4 mu m;
(C) stacking a plurality of ceramic thin strips in a staggered mode to enable a plurality of nickel electrode paste layers to be stacked at intervals in a staggered mode, performing pressurized lamination combination, and then cutting to form a green body of the laminated ceramic capacitor, wherein one side edge of each nickel electrode paste layer is exposed out of the opposite two sides of the green body in a staggered mode;
(D) dipping the opposite two sides of the green body in a second nickel electrode paste, coating the second nickel electrode paste with a predetermined thickness, and drying the second nickel electrode paste, wherein the second nickel electrode paste comprises nickel powder and barium titanate powder, and the average particle size of the nickel powder is 0.2-0.4 μm;
(E) then, the green body and the second nickel electrode paste on the two end surfaces are sintered by a common sintering mode, so that the green body is sintered and formed into a base part of the laminated ceramic capacitor, the plurality of ceramic thin strips are sintered and formed into a plurality of ceramic inductors of the base part, the plurality of first nickel electrode pastes are sintered and formed into a plurality of internal electrodes of the base part, the second nickel electrode paste is sintered and formed into a first external electrode of an external electrode layer, and the end parts of the internal electrodes, exposed out of the opposite two side edges of the base part, of the plurality of internal electrodes are in electrical contact with the first external electrode;
(F) and then forming resin containing metal electrode paste at the opposite outer sides of the two first external electrodes, and curing and forming to form the second external electrodes.
The method for manufacturing a multilayer ceramic capacitor, wherein: the volume percentage of the barium titanate powder to the nickel powder of the first nickel electrode paste in the step (B) and the volume percentage of the barium titanate powder to the nickel powder of the second nickel electrode paste in the step (D) are the same and are 15-50 vol%.
The method for manufacturing a multilayer ceramic capacitor, wherein: the second nickel electrode paste is sintered to form the first external electrode of the external electrode layer, and the thickness of the first external electrode is 5 to 50 μm.
Compared with the prior art, the invention adopting the technical scheme has the advantages that:
the main advantages of the present invention are that the base of the ceramic capacitor comprises ceramic dielectric and plural internal electrodes formed in the ceramic dielectric in staggered and spaced arrangement, and one side of the plural internal electrodes is respectively provided with an internal electrode end exposed outside the ceramic dielectric, and the internal electrode contains nickel powder and barium titanate powder with average particle size of 0.2 μm-0.4 μm, and two first external electrodes of external electrode layers are sintered on two sides of the base, and the two first external electrodes are in electric contact with the internal electrode end of the plural internal electrodes, and the first external electrode contains nickel powder and barium titanate powder with average particle size of 0.2 μm-0.4 μm, and a second external electrode made of metal powder and resin is formed outside the two first external electrodes, because both the internal electrode and the first external electrode contain nickel powder and barium titanate powder with average particle size of 0.2 μm-0.4 μm, therefore, the internal electrode and the first external electrode can be in good electrical contact, the mutual bonding strength can be improved, the occurrence of the situation that the first external electrode is stripped from the internal electrode is reduced, the electroplating solution is prevented from invading, and the purposes of improving the product yield and increasing the market competitiveness are achieved.
The second advantage of the present invention is that the volume percentage of nickel powder to barium titanate powder in the second nickel electrode paste is preferably the same as the volume percentage of nickel powder to barium titanate powder in the first nickel electrode paste, so that the volume change tends to be the same or similar when the multilayer ceramic capacitor is heated and expanded, thereby avoiding the damage caused by thermal expansion, and the first nickel electrode paste can be used as the second nickel electrode paste, thus achieving the purpose of reducing the material manufacturing time, waste and inventory.
Another advantage of the present invention is that the base and the first external electrode of the external electrode layer are made by co-sintering, which can effectively reduce the structural damage caused by the subsequent heating times or temperature to the capacitor itself or the end of the internal electrode of the plurality of internal electrodes, so as to prevent the first external electrode from being fragile or cracked, and further increase the compactness, thereby achieving the purpose of increasing the electrical contact between the two first external electrodes and the plurality of internal electrodes.
The metal powder in the metal electrode paste can be silver powder, silver and nickel mixed powder, copper powder covered with silver or other conductive powder, the resin comprises epoxy resin and thermosetting resin, and the second external electrode is cured and molded at about 250 ℃, so that the metal powder can not diffuse or invade to the positions of the two first external electrodes, the ceramic dielectric body or the internal electrode when the second external electrode is molded, and the purpose of not influencing the structural strength or the electrical conductivity of the first external electrode, the ceramic dielectric body or the internal electrode can be achieved.
Drawings
FIG. 1 is a side sectional view of the present invention.
Fig. 2 is a flow chart of the present invention.
FIG. 3 is a graph (one) showing the results of the measurement of the electrostatic capacity and the insulation resistance cracking rate of the present invention.
FIG. 4 is a graph showing the results of measurement of electrostatic capacity and insulation resistance cracking rate of the present invention (II).
Description of reference numerals: 1-a base; 11-a ceramic dielectric; 12-an inner electrode; 121-inner electrode tip; 2-external electrode layer; 21-a first external electrode; 22-a second external electrode; 23-third external electrode.
Detailed Description
To achieve the above objects and advantages, the present invention provides a technical solution and a structure thereof, which are described in detail with reference to the preferred embodiments of the present invention, and the features and functions thereof are fully understood.
Referring to FIG. 1, which is a side sectional view of the present invention, it can be clearly seen that the multilayer ceramic capacitor includes a base portion 1 and external electrode layers 2 formed on two sides of the base portion 1, wherein:
the base 1 comprises a ceramic dielectric body 11 and a plurality of internal electrodes 12 formed in the ceramic dielectric body 11 and arranged in a staggered manner, wherein one side of the plurality of internal electrodes 12 is respectively provided with an internal electrode end 121 exposed outside the ceramic dielectric body 11, the internal electrode ends 121 of the plurality of internal electrodes 12 are respectively exposed at two opposite sides of the ceramic dielectric body 11 in a staggered manner, and the internal electrodes 12 contain nickel powder and barium titanate powder with the average particle size of 0.2-0.4 μm.
The external electrode layer 2 includes a first external electrode 21 formed on both sides of the ceramic dielectric body 11 of the base 1, a second external electrode 22 formed on the outside of the first external electrode 21 on both sides, and a third external electrode 23 formed on the outside of the second external electrode 22, wherein the second external electrode 21 is in electrical contact with the internal electrode end 121 of the plurality of internal electrodes 12, the first external electrode 21 contains nickel powder and barium titanate powder having an average particle size of 0.2 μm to 0.4 μm, and the second external electrode 22 is formed by solidifying components such as metal powder and resin.
The ceramic dielectric 11 of the base 1 includes barium titanate powder, manganese oxide powder, yttrium oxide powder, silicon oxide powder, resin, and the like.
Further, the average particle diameter of the barium titanate powder contained in the internal electrode 12 of the base 1 and the first external electrode 21 of the external electrode layer 2 is 0.05 to 0.1 μm, and the volume percentage of the barium titanate powder to the nickel powder in the internal electrode 12 may be 25 vol%, and the volume percentage of the barium titanate powder to the nickel powder in the first external electrode 21 is 15 to 50 vol%.
The second external electrodes 22 of the external electrode layer 2 are composed of metal powder, such as silver powder, mixed powder of silver and nickel, copper powder coated with silver, or other conductive powder, and resin including epoxy resin and thermosetting resin (such as urea formaldehyde or phenol formaldehyde resin).
However, the third external electrode 23 of the external electrode layer 2 is a plating layer formed by plating mainly nickel, tin, or the like.
Referring to fig. 2, which is a flow chart of the present invention, it can be clearly seen that the method for manufacturing the multilayer ceramic capacitor of the present invention comprises the following steps:
(A) the ceramic slurry can be processed and formed into a ceramic thin strip by a thin strip forming machine.
(B) And processing and forming the first nickel electrode paste on the ceramic thin strip so as to form a nickel electrode paste layer on the ceramic thin strip, and drying the nickel electrode paste layer, wherein the first nickel electrode paste comprises nickel powder and barium titanate powder, and the average particle size of the nickel powder is 0.2-0.4 mu m.
(C) Then, stacking a plurality of ceramic thin bands in a staggered mode to enable a plurality of nickel electrode paste layers to be alternately stacked in a staggered mode, performing pressurized lamination and combination, and then cutting to form a green body of the laminated ceramic capacitor, wherein one side edge of each nickel electrode paste layer is exposed out of the opposite two sides of the green body in a staggered mode.
(D) The opposite two sides of the green body are dipped in a second nickel electrode paste, and then the green body is coated with a predetermined thickness and dried, wherein the second nickel electrode paste comprises nickel powder and barium titanate powder, and the average particle size of the nickel powder is between 0.2 and 0.4 mu m.
(E) Then, the green body and the second nickel electrode paste on the two end surfaces are sintered by a common sintering method to form the base part 1 of the multilayer ceramic capacitor by sintering the green body, the plurality of ceramic thin strips are sintered to form the plurality of ceramic dielectric bodies 11 of the base part 1, the plurality of first nickel electrode pastes are sintered to form the plurality of internal electrodes 12 of the base part 1, the second nickel electrode paste is sintered to form the first external electrodes 21 of the external electrode layer 2, and the internal electrode end parts 121 of the plurality of internal electrodes 12 exposed at the two opposite sides of the base part 1 are electrically contacted with the first external electrodes 21.
(F) Then, the metal electrode paste is formed on the opposite outer sides of the two first external electrodes 21, and the first external electrodes 21 are cured and formed into the second external electrodes 22.
(G) The third external electrode 23 is formed by electroplating the second external electrode 22, thereby completing the manufacture of the multilayer ceramic capacitor.
Step (a01) may be performed before step (a):
(A01) a ceramic slurry is prepared by taking a predetermined weight of main component (mainly barium titanate), adding other components (such as manganese oxide powder, yttrium oxide powder or silicon oxide powder) and solvent (composed of ethanol and toluene) and plasticizer, and processing and mixing by a ball mill.
The ceramic slurry in the step (A) is prepared by forming a ceramic thin strip with a width of about 150mm and a thickness of about 10 μm on a plastic film (such as a PET film) by a doctor blade of a thin strip forming machine, preferably a ceramic thin strip with a width of about 150mm and a thickness of about 6 μm, and then using the ceramic thin strip to prepare a 10 μ F capacitor with a size of 3225.
The first nickel electrode paste in the step (B) may be formed by screen printing a nickel electrode paste layer on the ceramic thin strip, and the first nickel electrode paste may include nickel powder, barium titanate powder, a binder, a solvent, and the like, wherein the barium titanate powder has an average particle size of 0.05 μm to 0.1 μm, and a volume percentage of the nickel powder to the barium titanate powder is about 25 vol%.
The ceramic thin strip in the step (C) may be cut into a size of about 150mm by 150 mm.
However, before the step (D) is performed, the step (D01) may be further performed:
(D01) the green body and the food powder are filled in a container, and the container is rotated to grind each corner portion of the green body.
The second nickel electrode paste in the step (D) comprises nickel powder, barium titanate powder, a binder, a solvent and other components, the average particle size of the barium titanate powder is 0.05-0.1 μm, the volume percentage of the nickel powder to the barium titanate powder is 15-50 vol%, and the volume percentage of the nickel powder to the barium titanate powder in the second nickel electrode paste is preferably the same as the volume percentage of the nickel powder to the barium titanate powder in the first nickel electrode paste, so that when the multilayer ceramic capacitor is heated and expanded, the volume change tends to be the same or similar, further the damage caused by thermal expansion is avoided, and the first nickel electrode paste can be used as the second nickel electrode paste, thus reducing the material manufacturing time, waste and inventory.
In addition, the thickness of the second nickel electrode paste in the step (D) is 5 μm to 50 μm to maintain the relatively stable electrical characteristics of the multilayer ceramic capacitor, and when the thickness of the second nickel electrode paste exceeds 50 μm, the first external electrodes 21 may be peeled off after the sintering of the two first external electrodes 21 of the external electrode layers 2, and when the thickness of the second nickel electrode paste is less than 5 μm, the electrical connection between the two first external electrodes 21 and the inner electrode ends 121 of the plurality of inner electrodes 12 may be insufficient, and the sintered product may not have the stable electrical characteristics.
After the second nickel electrode pastes are respectively formed on the two opposite side edges of the green body in the step (E), the green body and the second nickel electrode pastes on the two end surfaces can be placed in a nitrogen environment, degreasing treatment is carried out at the temperature of about 400 ℃, and the content of hydrogen/water vapor is controlled, so that the green body and the second nickel electrode pastes are subjected to common sintering operation at the temperature of about 1300 ℃ under the sintering condition of a low-reducing atmosphere which is more than one digit lower than the equilibrium oxygen partial pressure of nickel; however, when the first external electrodes 21 of the external electrode layer 2 are formed by sintering at about 1300 ℃ on both sides of the base 1, the first external electrodes 21 are not brittle or cracked, and the density of the sintered first external electrodes 21 is excellent, so that the two first external electrodes 21 can be electrically conducted with the inner electrode ends 121 of the plurality of internal electrodes 12 sufficiently, thereby improving the stability of electrical conduction, and the structural damage caused by the subsequent heating times or temperature to the capacitor itself or the inner electrode ends 121 of the plurality of internal electrodes 12 can be effectively reduced by using the common sintering method; in addition, the degreasing condition may be determined by using a proper condition for the kind of the binder and the plasticizer, and the maximum sintering temperature may be determined by the kind of the ceramic material to obtain a sufficient density, however, in the case of the atmosphere, if the sintering operation is performed in the atmosphere in which nickel is oxidized, the second external electrodes 21 of the external electrode layers 2 are acidified, and thus, sufficient conduction cannot be obtained, which is a necessity to be noted.
The metal electrode paste in the step (F) may be directly applied to the opposite sides of the two first external electrodes 21, or the two first external electrodes 21 are immersed in the metal electrode paste, so that the metal electrode paste is formed at the opposite outer sides of the two first external electrodes 21, and the two side metal electrode pastes may be heated or placed in an environment at a temperature of about 250 ℃ to be cured and formed into the second external electrodes 22.
The metal electrode paste in the step (F) includes metal powder, resin and other components, and can be dried at a temperature of about 100-150 ℃/30 minutes in the atmospheric environment, and then the metal electrode paste is cured and formed at a temperature of 220-270 ℃ in the atmospheric environment, so that the second external electrode 22 is formed by curing, and the temperature for curing and forming the metal electrode paste is preferably 240-270 ℃, so that the base 1 and the two first external electrodes 21 of the external electrode layer 2 can be sufficiently fixed, have adhesive strength and have a good electrical conduction state; the metal powder in the metal electrode paste may be silver powder, silver/nickel mixed powder, copper powder with silver coated on the surface, or other conductive powder, and the resin includes epoxy resin and thermosetting resin (such as urea formaldehyde or phenol formaldehyde resin), and the second external electrode 22 is cured and molded at about 250 ℃, so that the metal powder is prevented from diffusing or invading the positions of the two first external electrodes 21, the ceramic dielectric body 11 or the internal electrode 12, and the performance of the first external electrode 21, the ceramic dielectric body 11 or the internal electrode 12, such as structural strength or electrical conductivity, is not affected.
The second external electrode 22 in the step (G) is formed by electroplating with a third external electrode 23 through nickel and tin, so that the first external electrode 21, the second external electrode 22 and the third external electrode 23 of the external electrode layer 2 are respectively formed on two sides of the base 1, thereby manufacturing the multilayer ceramic capacitor, and improving the structural strength and reliability of the multilayer ceramic capacitor; in addition, since the resin material in the second external electrode 22 has a special property of blocking diffusion of the metal element, when the third external electrode 23 is formed by electroplating outside the second external electrode 22 on both sides of the base 1, the plating solution of the third external electrode 23 does not intrude into the positions of the second external electrode 22, the first external electrode 21, the ceramic dielectric 11, the internal electrode 12, and the like, so that the existing structural strength of the multilayer ceramic capacitor can be maintained, and the multilayer ceramic capacitor has a good capacitor performance.
In order to verify the capacitance strength and reliability of the multilayer ceramic capacitor manufactured according to the present invention, the nickel powder and the barium titanate powder in the internal electrode 12 of the base 1 and the first external electrode 21 of the external electrode layer 2 according to the present invention were selected to be matched in three different particle sizes, and the nickel powder and the barium titanate powder in the first external electrode 21 were respectively tested according to different volume percentage ratios, and the results of the electrostatic capacitance and the insulation resistance cracking rate of different first external electrode thicknesses after firing were compared, and all the test results are shown in the third and fourth graphs.
The first collocation method comprises the following steps: the average particle size of the nickel powder in the internal electrode 12 was 0.4 μm and the average particle size of the barium titanate powder was 0.1 μm, and the volume percentage ratio of the barium titanate powder to the nickel powder was 25 vol%, and the average particle size of the nickel powder in the first external electrode 21 was 0.4 μm and the average particle size of the barium titanate powder was 0.1 μm.
And (2) second matching: the average particle size of the nickel powder in the internal electrode 12 was 0.2 μm and the average particle size of the barium titanate powder was 0.05 μm, and the volume percentage ratio of the barium titanate powder to the nickel powder was 25 vol%, and the average particle size of the nickel powder in the first external electrode 21 was 0.4 μm and the average particle size of the barium titanate powder was 0.1 μm.
And (3) matching: the average particle size of the nickel powder in the internal electrode 12 was 0.2 μm and the average particle size of the barium titanate powder was 0.05 μm, and the volume percentage ratio of the barium titanate powder to the nickel powder was 25 vol%, and the average particle size of the nickel powder in the first external electrode 21 was 0.2 μm and the average particle size of the barium titanate powder was 0.05 μm.
It is clear from the above three combinations that when the nickel powder with an average particle size of 0.2-0.4 μm and the barium titanate powder with an average particle size of 0.05-0.1 μm are used for the inner electrode 12 and the nickel powder with an average particle size of 0.2-0.4 μm and the barium titanate powder with an average particle size of 0.05-0.1 μm are used for the first outer electrode 21, the first outer electrode 21 is not peeled within a range of 5-50 μm in average thickness after sintering, the electrostatic capacity can reach more than 10 μ F, the volume ratio of the barium titanate powder to the nickel powder in the first outer electrode 21 can be used within a composition range of 15-50 vol%, and the reliability test result in 1000 hours shows that none of the 80 test pieces has defects or insulation resistance cracking.
The invention has the following advantages:
the internal electrode and the first external electrode both contain nickel powder and barium titanate powder with the average particle size of 0.2-0.4 mu m, so that the internal electrode and the first external electrode have good electrical contact, the mutual bonding strength can be improved, the situation that the first external electrode is stripped from the internal electrode is reduced, the electroplating solution is prevented from invading, and the effects of improving the product percent of pass and increasing the market competitiveness are achieved.
The volume percentage of nickel powder to barium titanate powder in the second nickel electrode paste is better to be the same as that of the nickel powder to barium titanate powder in the first nickel electrode paste, so that when the multilayer ceramic capacitor is heated and expanded, the volume change tends to be the same or similar, further the structural damage caused by thermal expansion is avoided, and the first nickel electrode paste can be used as the second nickel electrode paste, thus achieving the effect of reducing the manufacturing time, waste and stock of materials.
Thirdly, the base 1 and the first external electrodes 21 of the external electrode layer 2 are made by co-sintering, which can effectively reduce the structural damage caused by the subsequent heating times or temperature to the capacitor itself or the internal electrode end 121 of the plurality of internal electrodes 12, so that the first external electrodes 21 are not fragile or cracked, and the compactness is further improved, thereby achieving the effect of improving the electrical contact between the two first external electrodes 21 and the plurality of internal electrodes 12.
And (IV) the metal powder in the metal electrode paste can be silver powder, silver and nickel mixed powder, copper powder with silver covered on the surface or other conductive powder, the resin comprises epoxy resin and thermosetting resin, and the second external electrode 22 is cured and molded at the temperature range of about 250 ℃, so that the metal powder can be ensured not to diffuse or invade to the positions of the two first external electrodes 21, the ceramic dielectric bodies 11 or the internal electrodes 12 and the like when the second external electrode 22 is molded, and the performances of structural strength, electric conduction and the like of the first external electrodes 21, the ceramic dielectric bodies 11 or the internal electrodes 12 and the like are not influenced.
The foregoing description is intended to be illustrative rather than limiting, and it will be appreciated by those skilled in the art that many modifications, variations or equivalents may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A multilayer ceramic capacitor, characterized in that: comprises a base part and external electrode layers formed on two sides of the base part, wherein:
the base comprises a ceramic dielectric body and a plurality of internal electrodes which are formed in the ceramic dielectric body and are arranged in a staggered and spaced mode, one side edge of each internal electrode is provided with an end part of the internal electrode which is exposed out of the ceramic dielectric body, and the internal electrodes contain nickel powder and barium titanate powder with the average grain diameter of 0.2-0.4 mu m;
the external electrode layer comprises first external electrodes which are sintered and formed at two sides of the ceramic dielectric body of the base part and second external electrodes which are formed at the outsides of the first external electrodes at two sides, wherein the two first external electrodes are in electrical contact with the end parts of the internal electrodes of the plurality of internal electrodes, the first external electrodes contain nickel powder and barium titanate powder with the average particle size of 0.2-0.4 mu m, the second external electrodes are formed by metal powder and resin, and the average thickness of the first external electrodes is 5-50 mu m;
wherein the volume percentage of barium titanate powder to nickel powder in the internal electrode of the base part and the first external electrode of the external electrode layer is the same.
2. The multilayer ceramic capacitor according to claim 1, wherein: the base part and the two first external electrodes of the external electrode layer are sintered by a co-sintering method.
3. The multilayer ceramic capacitor according to claim 1, wherein: the barium titanate powder contained in the internal electrode of the base portion and the first external electrode of the external electrode layers has an average particle diameter of 0.05 to 0.1 [ mu ] m.
4. The multilayer ceramic capacitor of claim 1, wherein: the volume percentage of barium titanate powder to nickel powder in the first external electrode of the external electrode layer is 15 vol% -50 vol%.
5. The multilayer ceramic capacitor according to claim 1, wherein: the metal powder of the second external electrode is silver powder, silver-nickel mixed powder, copper powder or copper powder with the surface covered by silver, and the resin comprises epoxy resin and thermosetting resin.
6. A method for manufacturing a multilayer ceramic capacitor, comprising the steps of:
(A) firstly, processing and molding the ceramic slurry into a ceramic thin strip by using a thin strip molding machine;
(B) processing and forming a first nickel electrode paste on the ceramic thin strip so as to form a nickel electrode paste layer on the ceramic thin strip, and drying the nickel electrode paste layer, wherein the first nickel electrode paste comprises nickel powder and barium titanate powder, the average particle size of the nickel powder is 0.2-0.4 mu m, and the volume percentage of the barium titanate powder to the nickel powder of the first nickel electrode paste is the same and is 15-50 vol%;
(C) stacking a plurality of ceramic thin strips in a staggered manner so that a plurality of nickel electrode paste layers are alternately stacked in a staggered manner, performing pressurized lamination combination, and then cutting to form a green body of the laminated ceramic capacitor, wherein one side edge of each nickel electrode paste layer is exposed out of the opposite two sides of the green body in a spaced and staggered manner;
(D) immersing the opposite two sides of the green body in a second nickel electrode paste, coating the second nickel electrode paste with a predetermined thickness, and drying the second nickel electrode paste, wherein the second nickel electrode paste comprises nickel powder and barium titanate powder, the average particle size of the nickel powder is 0.2-0.4 mu m, and the volume percentage of the barium titanate powder to the nickel powder of the second nickel electrode paste is the same and is 15-50 vol%; the second nickel electrode paste is sintered to form a first external electrode of the external electrode layer, and the thickness of the first external electrode is 5-50 mu m;
(E) then, the green body and the second nickel electrode paste on the two end surfaces are sintered by a common sintering mode, so that the green body is sintered and formed into a base part of the laminated ceramic capacitor, the plurality of ceramic thin strips are sintered and formed into a plurality of ceramic inductors of the base part, the plurality of first nickel electrode pastes are sintered and formed into a plurality of internal electrodes of the base part, the second nickel electrode paste is sintered and formed into a first external electrode of an external electrode layer, and the end parts of the internal electrodes, exposed out of the opposite two side edges of the base part, of the plurality of internal electrodes are in electrical contact with the first external electrode;
(F) and then forming resin containing metal electrode paste at the opposite outer sides of the two first external electrodes, and curing and forming the second external electrodes.
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| JP2011018898A (en) * | 2009-06-08 | 2011-01-27 | Daiken Chemical Co Ltd | Barium titanate powder, nickel paste, manufacturing method, and laminated ceramic capacitor |
| CN102201284A (en) * | 2010-03-23 | 2011-09-28 | 三星电机株式会社 | Multilayer ceramic capacitor with Y5V characteristic |
| CN108364786A (en) * | 2017-01-25 | 2018-08-03 | 禾伸堂企业股份有限公司 | Multilayer ceramic capacitor and method for manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011018898A (en) * | 2009-06-08 | 2011-01-27 | Daiken Chemical Co Ltd | Barium titanate powder, nickel paste, manufacturing method, and laminated ceramic capacitor |
| TW201108250A (en) * | 2009-06-08 | 2011-03-01 | Daiken Chemical Co Ltd | Barium titanate powder, nickel paste, their production method and multilayer ceramic capacitor |
| CN102201284A (en) * | 2010-03-23 | 2011-09-28 | 三星电机株式会社 | Multilayer ceramic capacitor with Y5V characteristic |
| CN108364786A (en) * | 2017-01-25 | 2018-08-03 | 禾伸堂企业股份有限公司 | Multilayer ceramic capacitor and method for manufacturing same |
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