CN102270535A - Method for manufacturing polymer ethylenedioxythiophene (PEDT) cathode plate type tantalum electrolytic capacitor by two-step method - Google Patents
Method for manufacturing polymer ethylenedioxythiophene (PEDT) cathode plate type tantalum electrolytic capacitor by two-step method Download PDFInfo
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Abstract
The invention discloses a method for manufacturing a polymer ethylenedioxythiophene (PEDT) cathode plate type tantalum electrolytic capacitor by a two-step method. The cathode plate type tantalum electrolytic capacitor is manufactured by adopting the two-step method. The two-step method is a method which comprises the following steps of: impregnating an oxidizing agent at the first time, impregnating a monomer at the second time, and polymerizing the oxidizing agent and the monomer to prepare PEDT so as to manufacture the cathode plate type tantalum electrolysis capacitor, wherein the whole process is performed under normal temperature. The manufacturing method comprises the following steps of: A, adding a certain amount of adhesive agent into tantalum powder, and stamping and molding the mixture, sintering the treated mixture at high temperature to volatilize the adhesive agent and effectively adhere the tantalum powder so as to form a multi-hole tantalum anode plate, and applying direct-current voltage in acidic solution, so that the surface of the tantalum powder is oxidized to generate an amorphous dielectric layer Ta2O5; B, repeatedly immersing the anode plate with the dielectric layer in the oxidizing agent and monomer solution for reaction so as to form a conducting polymer PEDT layer with a certain thickness, namely a cathode; and C, immersing the anode block with the PEDT layer in graphite and silver slurry respectively, curing respectively at high temperature, and performing assembly, plastic package, aging test and labeling to package a capacitor product.
Description
Technical field
The present invention relates to a kind of manufacture method of tantalum capacitor, the manufacture method of especially ultralow ESR value PEDT negative electrode sheet type tantalum electrolyte capacitor; Belong to the power electronic device technical field.
Background technology
The store charge that the electrode that capacitor conductor that is generally all approaching by two and mutually insulated is made is formed and the device of electric energy.It is widely used in every aspects such as straight, coupling, bypass, filtering, resonant tank, power conversion, control circuits.
The chip-type solid tantalum electrolytic capacitor is to be positive pole with valve metal T tantalum, forms the Ta of impalpable structure at tantalum surface by anodic oxidation
2O
5Layer adds negative electrode layer and constitutes as dielectric.At present domestic sheet type tantalum electrolyte capacitor is all with MnO
2As negative pole, frequency of utilization is generally below 10 MHz, but along with the electronic technology high speed development of Switching Power Supply high frequencyization, miniaturization particularly, solid tantalum capacitor has been proposed the strict demand of low impedance at high frequency electrical property, will have the performance of anti-high ripple current simultaneously.Solid tantalum capacitor is because MnO
2The reason of material self character makes that product E SR is higher, can not adapt in HF link.
In addition, MnO
2Tantalum electric capacity can make the whole capacitor catching fire owing to contain higher oxygen in the negative pole when losing efficacy puncture.Jeopardize the electronic devices and components of periphery, damage range is enlarged.
These defectives have seriously limited the application of solid tantalum capacitor.
Summary of the invention
Goal of the invention of the present invention is exactly higher in order to solve existing tantalum electric capacity ESR, and contain higher oxygen in the negative pole, can make the deficiency of whole capacitor catching fire when losing efficacy puncture, propose a kind of new tantalum electrolytic capacitor manufacture method, this tantalum electrolytic capacitor manufacture method can reduce Ta
2O
5The destruction of dielectric layer, and the I of ESR(that can significantly reduce capacitor reaches 4m Ω), improve the high frequency characteristics of capacitor.
Technology implementation method of the present invention is: a kind of two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacture method, adopt two-step method to make cathode sheets formula tantalum electrolytic capacitor (so-called two-step method, refer in particular to negative electrode PEDT forming process, for the one-step method that some documents are mentioned both at home and abroad at present), described two-step method is to adopt first impregnation oxidant, the impregnation monomer makes it polymerization and forms the method that PEDT makes the negative electrode sheet type tantalum electrolyte capacitor again; Overall process is all reacted under normal temperature condition, and reaction speed is controlled easily, and polymer forms and also has clear improvement the relative homogeneous of PEDT thickness than one-step method.
Described two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacturing approach craft comprises:
A: the tantalum powder is added a certain amount of adhesive moulded section, and high temperature sintering volatilization adhesive also makes the tantalum powder that effective adhesive be arranged, and forms the tantalum anode piece of porous, applies the direct voltage electrolysis again and make tantalum powder surface oxidation generate amorphous dielectric layer Ta in acid solution
2O
5
B: the anode block that will generate dielectric layer immerses oxidant and monomer solution reaction repeatedly and forms and have certain thickness conducting polymer PEDT layer, i.e. negative pole;
C: the anode block that will generate the PEDT layer immerses graphite, silver slurry and difference hot setting respectively, and assembling then, plastic packaging, burn-in test, mark are packaged into capacitor product.
Wherein, described steps A specifically comprises:
A1: adhesive is added the tantalum powder in the 1-5% ratio, with 4.0-8.0g/cm
3Pressed density moulded section (band tantalum line draw), and in vacuum furnace high temperature sintering (temperature 1100-1900 ℃, vacuum degree〉3 * 10
-4Pa, time 2-6 hour) releasing adhesive obtains the tantalum powder particles anode bodies adhered to one another of porous.
A2: according to the suitable electrolyte (0.1-5%H of product voltage different choice
3PO
440-80% ethylene glycol or polyethylene glycol, surplus is a water), doubly select the suitable direct current voltage of energizing with electrochemical method according to the 3-5 of product rated voltage, current density 10-100mA/g forms the amorphous Ta that one deck has certain intensity and thickness on anode bodies tantalum powder particles surface
2O
5Dielectric layer.
Described step B is the core content of this invention, this step forms the conducting polymer negative electrode layer of tantalum electric capacity, its conductivity is 1～100 S/cm, conductivity (0.1 S/cm) far above traditional capacitor negative pole manganese dioxide, therefore obtain the capacitor of extremely low ESR easily, high frequency performance significantly promotes.Specifically comprise following technology:
B1: the preparation mass concentration is the aqueous solution a of 10-50% p-methyl benzenesulfonic acid iron;
B2: the preparation mass concentration is the ethanolic solution b of 20-60% 3,4 enedioxy thiophene;
B3: will form dielectric layer Ta
2O
5Anode bodies insert the impregnation of a solution and take out after 5 minutes, and kept at room temperature 120 minutes so that solution fully immerses porous anode body;
B4: the product of step B3 is inserted b solution impregnation 50-65 take out after second, and keep 85-95 minute at room temperature, generate our needed conducting polymer PEDT so that monomer and oxide fully react;
B5: the polymerization pellet of above-mentioned steps B4 is put into the methanol solution flushing take out after 25-35 minute;
B6: the deionized water flushing of the pellet of above-mentioned B5 being put into again 15-25 ℃ was taken out after 25-35 minute;
B7: the pellet of above-mentioned B6 is put into H
3PO
4Concentration is to mend in the solution of 0.1-5% to form 25-35 minute, applies 1.5-3 product rated voltage doubly;
B8: the pellet after the benefit formation of above-mentioned B7 is put into pure water cleaned 25-35 minute, to remove residual H
3PO
4Solution.
B9: the pellet after will washing is put into methanol solution and is cleaned to take out after 25-35 minute and dried at ambient temperature 45-55 minute
Repeating above-mentioned steps B3-B9, is 10-100 μ m up to the outside covering of anode bodies PEDT thickness.
Described step C specifically comprises:
C1: the anode block that has the PEDT negative pole that above-mentioned steps B is formed immerses graphite solution 3-10 minute that viscosity is 50-200cps, solidifies 10-30 minute down at 100-150 ℃, is cooled to room temperature then;
C2: it is conductive silver paste 2-8 minute of 1000-2500cps that the sample of step C1 is immersed viscosity, solidifies 10-30 minute down at 120-160 ℃, is cooled to room temperature then;
The sample of C3: step C2 is welded on the tantalum line on the leadframe and forms positive pole and draw, and simultaneously negative electrode is formed negative pole by the conductive silver adhesives on leadframe and draws.Oven dry was cooled to room temperature then with the curing of silver slurry in 10-30 minute under 100-160 ℃ of temperature;
C4: the sample of step C3 is carried out plastic packaging by the high temperature plastic packaging machine;
C5: the production that the sample of step C4 is promptly finished all process steps by burn-in test and mark encapsulation obtains the macromolecule chip tantalum capacitor.
The present invention utilizes macromolecule PEDT to replace traditional MnO
2As the cathode material of tantalum capacitor, polymerization reaction all forms at normal temperatures, has reduced Ta
2O
5The destruction of dielectric layer.Simultaneously because the characteristic of PEDT itself is compared MnO
2The I of ESR(that capacitor significantly reduces capacitor reaches 4m Ω), improved the high frequency characteristics of capacitor.It is higher to have solved chip tantalum electric capacity ESR, can not be applied to high-frequency circuit, and the danger that whole capacitor can be burnt when losing efficacy.
Description of drawings
Fig. 1 is PEDT and MnO
2The frequency capability variation relation figure of tantalum capacitor;
Fig. 2 is the manufacturing process flow diagram of macromolecule tantalum capacitor of the present invention.
Embodiment
The present invention will be further described below in conjunction with the drawings and specific embodiments.
By accompanying drawing 1 as can be seen, with traditional MnO
2Tantalum electrolytic capacitor is compared, the invention provides a kind of brand-new cathode material manufacture method, be a kind of two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacture method, adopt two-step method to make cathode sheets formula tantalum electrolytic capacitor (so-called two-step method, refer in particular to negative electrode PEDT forming process, for the one-step method that some documents are mentioned both at home and abroad at present), described two-step method is to adopt first impregnation oxidant, the impregnation monomer makes it polymerization and forms the method that PEDT makes the negative electrode sheet type tantalum electrolyte capacitor again; Overall process is all reacted under normal temperature condition, and reaction speed is controlled easily, and polymer forms and also has clear improvement the relative homogeneous of PEDT thickness than one-step method.
Described two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacturing approach craft comprises as shown in Figure 2:
A: the tantalum powder is added a certain amount of adhesive moulded section, and high temperature sintering volatilization adhesive also makes the tantalum powder that effective adhesive be arranged, and forms the tantalum anode piece of porous, applies the direct voltage electrolysis again and make tantalum powder surface oxidation generate amorphous dielectric layer Ta in acid solution
2O
5
B: the anode block that will generate dielectric layer immerses oxidant and monomer solution reaction repeatedly and forms and have certain thickness conducting polymer PEDT layer, i.e. negative pole;
C: the anode block that will generate the PEDT layer immerses graphite, silver slurry and difference hot setting respectively, and assembling then, plastic packaging, burn-in test, mark are packaged into capacitor product.
Wherein, described steps A specifically comprises:
A1: adhesive is added the tantalum powder in the 1-5% ratio, with 4.0-8.0g/cm
3Pressed density moulded section (band tantalum line draw), and in vacuum furnace high temperature sintering (temperature 1100-1900 ℃, vacuum degree〉3 * 10
-4Pa, time 2-6 hour) releasing adhesive obtains the tantalum powder particles anode bodies adhered to one another of porous.
A2: according to the suitable electrolyte (0.1-5%H of product voltage different choice
3PO
440-80% ethylene glycol or polyethylene glycol, surplus is a water), doubly select the suitable direct current voltage of energizing with electrochemical method according to the 3-5 of product rated voltage, current density 10-100mA/g forms the amorphous Ta that one deck has certain intensity and thickness on anode bodies tantalum powder particles surface
2O
5Dielectric layer.
Described step B is the core content of this invention, this step forms the conducting polymer negative electrode layer of tantalum electric capacity, its conductivity is 1～100 S/cm, conductivity (0.1 S/cm) far above traditional capacitor negative pole manganese dioxide, therefore obtain the capacitor of extremely low ESR easily, high frequency performance significantly promotes.Specifically comprise following technology:
B1: the preparation mass concentration is the aqueous solution a of 10-50% p-methyl benzenesulfonic acid iron;
B2: the preparation mass concentration is the ethanolic solution b of 20-60% 3,4 enedioxy thiophene;
B3: will form dielectric layer Ta
2O
5Anode bodies insert the impregnation of a solution and take out after 5 minutes, and kept at room temperature 120 minutes so that solution fully immerses porous anode body;
B4: the product of step B3 is inserted b solution impregnation 50-65 take out after second, and keep 85-95 minute at room temperature, generate our needed conducting polymer PEDT so that monomer and oxide fully react;
B5: the polymerization pellet of above-mentioned steps B4 is put into the methanol solution flushing take out after 25-35 minute;
B6: the deionized water flushing of the pellet of above-mentioned B5 being put into again 15-25 ℃ was taken out after 25-35 minute;
B7: the pellet of above-mentioned B6 is put into H
3PO
4Concentration is to mend in the solution of 0.1-5% to form 25-35 minute, applies 1.5-3 product rated voltage doubly;
B8: the pellet after the benefit formation of above-mentioned B7 is put into pure water cleaned 25-35 minute, to remove residual H
3PO
4Solution.
B9: the pellet after will washing is put into methanol solution and is cleaned to take out after 25-35 minute and dried at ambient temperature 45-55 minute
Repeating above-mentioned steps B3-B9, is 10-100 μ m up to the outside covering of anode bodies PEDT thickness.
Described step C specifically comprises:
C1: the anode block that has the PEDT negative pole that above-mentioned steps B is formed immerses graphite solution 3-10 minute that viscosity is 50-200cps, solidifies 10-30 minute down at 100-150 ℃, is cooled to room temperature then;
C2: it is conductive silver paste 2-8 minute of 1000-2500cps that the sample of step C1 is immersed viscosity, solidifies 10-30 minute down at 120-160 ℃, is cooled to room temperature then;
The sample of C3: step C2 is welded on the tantalum line on the leadframe and forms positive pole and draw, and simultaneously negative electrode is formed negative pole by the conductive silver adhesives on leadframe and draws.Oven dry was cooled to room temperature then with the curing of silver slurry in 10-30 minute under 100-160 ℃ of temperature;
C4: the sample of step C3 is carried out plastic packaging by the high temperature plastic packaging machine;
C5: the production that the sample of step C4 is promptly finished all process steps by burn-in test and mark encapsulation obtains the macromolecule chip tantalum capacitor.
Embodiment one
As positive pole, utilize electrolysis principle to form the unbodied Ta of one deck with valve metal tantalum powder adhered to one another behind the high temperature sintering on its surface
2O
5As dielectric, utilize method of the present invention to form then and have certain thickness conducting polymer as negative pole, encapsulated moulding at skin.
Present embodiment is with 10V47 μ F, and C shell polymer capacitor is an example, explains manufacturing process in detail:
1, anode forms: the tantalum powder of specific volume 32000 μ F.V/g is mixed 2% adhesive, press 6g/cm
3Pressed density compression moulding (φ 0.20mm tantalum line is drawn), in the vacuum sintering furnace 1400 ℃ high temperature sintering 25-35 minute.
2, dielectric layer forms: in 2% phosphoric acid solution, adopt the direct voltage of 40V, the current density of 50mA/g is energized, and constant voltage time 3 hours makes tantalum powder surface form Ta
2O
5
3, negative pole forms:
A: the p-methyl benzenesulfonic acid molten iron solution a of preparation mass concentration 20%;
B: 3,4 enedioxy thiophene ethanol solution b of preparation mass concentration 35%;
C: will form dielectric layer Ta
2O
5Anode bodies insert the impregnation of a solution and take out after 5 minutes, and kept at room temperature 120 minutes so that solution fully immerses porous anode body;
D: the product of step B3 is inserted the impregnation of b solution take out after 60 seconds, and keep 90 minutes at room temperature, generate our needed conducting polymer PEDT so that monomer and oxide fully react;
E: the polymerization pellet of above-mentioned steps D is put into the methanol solution flushing take out after 30 minutes;
F: the deionized water flushing of the pellet of above-mentioned E being put into again 20 ℃ was taken out after 30 minutes;
G: the pellet after will washing is put into H
3PO
4Concentration is to use the voltage of 25V to mend in 3% the solution to form 30 minutes, to repair in the above-mentioned polymerization process destruction to dielectric layer;
H: the pellet that will mend after forming is put into pure water cleaning 30 minutes, to remove residual H
3PO
4Solution;
I: the pellet after will washing is put into methanol solution and is cleaned to take out after 30 minutes and dried at ambient temperature 50 minutes
Repeat above-mentioned steps C-I, till the outside covering of anode bodies PEDT thickness is 10-100 μ m, this thickness can adopt SEM (scanning electron microscopy) to observe, mode has 2 kinds, 1 kind is the form that adopts DPA, adopt at a slow speed that the encapsulating resin is cured, adopt 60-4000 order abrasive paper for metallograph to carry out grinding and polishing on grinder successively, sample treatment is inserted the SEM sample room in the DPA surface gold-plating, after being coated with carbon, oven dry and is doubly measured down at 200-5000 afterwards; The 2nd kind of method is to utilize SEM secondary electron and backscattered electron image-forming principle difference to take pictures, the secondary electron imaging is suitable for the analysis to apparent pattern of microcosmic, and the backscattered electron imaging is suitable for the element distribution analysis of sample surfaces, in conjunction with Image J PaintShop the bat picture is carried out the distribution situation that pixel analysis can obtain polymer thickness.
4, negative pole solidifies:
A: the anode block that will have a PEDT negative pole immerses the graphite solution 5 minutes that viscosity is 120cps, 120 ℃ of oven dry 25 minutes down, is cooled to room temperature then.
B: the sample that will be coated with carbon immerses the conductive silver paste 8 minutes that viscosity is 1500cps, 150 ℃ down oven dry fully solidified in 30 minutes, be cooled to room temperature then.
5, both positive and negative polarity is drawn
The sample that is coated with silver is welded on the tantalum line on the leadframe forms positive pole and draw, simultaneously negative electrode is formed negative pole by the conductive silver adhesives on leadframe and draw.Dry 30 minutes down with the curing of silver slurry at 120 ℃, be cooled to room temperature then.
6, product plastic packaging
The product of step 5 is carried out plastic packaging by C shell high temperature plastic packaging machine, and hot setting becomes product approval.
7, aging, test, screening, mark encapsulation obtain 10V47 μ F, C shell polymer capacitor.
Cathode material not only has a strong impact on the temperature frequency characteristic of capacitance, loss angle tangent, equivalent series resistance and the impedance of tantalum electrolytic capacitor, and has a strong impact on leakage current, ripple characteristics, temperature characterisitic, useful life and the reliability of tantalum electrolytic capacitor.The macromolecule tantalum capacitor that utilizes this invention to make has very strong self-healing property, and can not produce the violent burning as the manganese dioxide capacitor when product failure.Also need not as the manganese dioxide capacitor derate in use and use too much, suggestion is to the product derate 10% of rated voltage less than 10 volts, to product derate 20% use of rated voltage greater than 10 volts.
Consider specification provided by the invention disclosed herein and embodiment, other embodiments of the present invention are apparent to those skilled in the art.Specification and embodiment only are used for example, represent the real scope and spirit of the present invention by claim.
Claims (7)
1. two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacture method, it is characterized in that: adopt two-step method to make cathode sheets formula tantalum electrolytic capacitor, described two-step method is to adopt first impregnation oxidant, the impregnation monomer makes it polymerization and forms the method that PEDT makes the negative electrode sheet type tantalum electrolyte capacitor again.
2. two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacture method according to claim 1, it is characterized in that: described method overall process is all reacted under normal temperature condition.
3. two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacture method according to claim 2, it is characterized in that: described method comprises the steps:
A, the tantalum powder is added a certain amount of adhesive moulded section, high temperature sintering volatilization adhesive also makes the tantalum powder that effective adhesive be arranged, and forms the tantalum anode piece of porous, applies the direct voltage electrolysis again and make tantalum powder surface oxidation generate amorphous dielectric layer Ta in acid solution
2O
5
B, the anode block that will generate dielectric layer immerse oxidant repeatedly and the monomer solution reaction forms certain thickness conducting polymer PEDT layer, i.e. negative pole;
C, the anode block that will generate the PEDT layer immerse graphite, silver slurry and hot setting respectively respectively, and assembling then, plastic packaging, burn-in test, mark are packaged into capacitor product.
4. two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacture method according to claim 3, it is characterized in that: described steps A specifically comprises:
A1: adhesive is added the tantalum powder in the 1-5% ratio, with 4.0-8.0g/cm
3Pressed density moulded section, and the high temperature sintering releasing adhesive obtains the tantalum powder particles anode bodies adhered to one another of porous in vacuum furnace;
A2: according to the suitable electrolyte of product voltage different choice, doubly select the suitable direct current voltage of energizing with electrochemical method according to the 3-5 of product rated voltage, current density 10-100mA/g forms the amorphous Ta that one deck has certain intensity and thickness on anode bodies tantalum powder particles surface
2O
5Dielectric layer.
5. two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacture method according to claim 4 is characterized in that: 1100-1900 ℃ of the middle high temperature sintering temperature in the steps A 1, vacuum degree〉3 * 10
-4Pa, time 2-6 hour; Electrolyte is 0.1-5%H among the A2
3PO
4, 40-80% ethylene glycol or polyethylene glycol, surplus is a water.
6. two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacture method according to claim 3, it is characterized in that: described step B specifically comprises following technology:
B1: the preparation mass concentration is the aqueous solution a of 10-50% p-methyl benzenesulfonic acid iron;
B2: the preparation mass concentration is the ethanolic solution b of 20-60% 3,4 enedioxy thiophene;
B3: will form dielectric layer Ta
2O
5Anode bodies insert the impregnation of a solution and take out after 5 minutes, and kept at room temperature 120 minutes so that solution fully immerses porous anode body;
B4: the product of step B3 is inserted b solution impregnation 50-65 take out after second, and keep 85-95 minute at room temperature, generate our needed conducting polymer PEDT so that monomer and oxide fully react;
B5: the polymerization pellet of above-mentioned steps B4 is put into the methanol solution flushing take out after 25-35 minute;
B6: the deionized water flushing of the pellet of above-mentioned B5 being put into again 15-25 ℃ was taken out after 25-35 minute;
B7: the pellet of above-mentioned B6 is put into H
3PO
4Concentration is to mend in the solution of 0.1-5% to form 25-35 minute, applies 1.5-3 product rated voltage doubly;
B8: the pellet after the benefit formation of above-mentioned B7 is put into pure water cleaned 25-35 minute, to remove residual H
3PO
4Solution;
B9: the pellet after will washing is put into methanol solution and is cleaned to take out after 25-35 minute and dried at ambient temperature 45-55 minute
Repeating above-mentioned steps B3-B9, is 10-100 μ m up to the outside covering of anode bodies PEDT thickness.
7. two-step method PEDT negative electrode sheet type tantalum electrolyte capacitor manufacture method according to claim 3, it is characterized in that: described step C specifically comprises:
C1: the anode block that has the PEDT negative pole that step B is formed immerses graphite solution 3-10 minute that viscosity is 50-200cps, solidifies 10-30 minute down at 100-150 ℃, is cooled to room temperature then;
C2: it is conductive silver paste 2-8 minute of 1000-2500cps that the sample of step C1 is immersed viscosity, solidifies 10-30 minute down at 120-160 ℃, is cooled to room temperature then;
The sample of C3: step C2 is welded on the tantalum line on the leadframe and forms positive pole and draw, and simultaneously negative electrode is formed negative pole by the conductive silver adhesives on leadframe and draws;
Oven dry was cooled to room temperature then with the curing of silver slurry in 10-30 minute under 100-160 ℃ of temperature;
C4: the sample of step C3 is carried out plastic packaging by the high temperature plastic packaging machine;
C5: the production that the sample of step C4 is promptly finished all process steps by burn-in test and mark encapsulation obtains the macromolecule chip tantalum capacitor.
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|---|---|---|---|
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| CN108906974A (en) * | 2017-07-27 | 2018-11-30 | 北京华宇创新钽铌科技有限公司 | Filmlubrication scheme in tantalum spinneret micropore punch process |
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| CN108906974A (en) * | 2017-07-27 | 2018-11-30 | 北京华宇创新钽铌科技有限公司 | Filmlubrication scheme in tantalum spinneret micropore punch process |
| CN109065376A (en) * | 2018-08-13 | 2018-12-21 | 福建国光电子科技股份有限公司 | A method of for processing solid-state capacitor cathode |
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