CN1776847A - Method for preparing solid electrolytic capacitor cathode - Google Patents
Method for preparing solid electrolytic capacitor cathode Download PDFInfo
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Abstract
The method includes manufacturing process and process conditions. Through solution of manganous nitrate, adulteration is carried out to improve wettability of surface of oxide film of medium. Thus, manganese dioxide in low resistivity is obtained after manganous nitrate is decomposed under high temperature. Finally, value of equivalent series resistance (ESR) of capacitor in high frequency is reduced greatly. Thus, ESR value of capacitor in 100 microfarad is under 0.075 ohm, which is about 1/3 value of capacitor produced under original process conditions. When measurement is carried at 100KHz.
Description
The technical field is as follows: the invention relates to an element of an electric appliance, in particular to a method for manufacturing a cathode of a solid electrolytic capacitor.
Background art: since electronic devices are continuously developing toward high frequency and small size, an equivalent string of one of the main parameters of the capacitor is requiredThe ESR value of the series resistance decreases. The invention patent "method for manufacturing solid electrolytic capacitor" application No. 200410079295.2 discloses a method for manufacturing a solid electrolytic capacitor using a valve metal such as tantalum, niobium, aluminum, titanium, etc. as an anode, which can make a manganese dioxide layer, a graphite layer, and a silver paste layer closely combined, enhance adhesion, and effectively reduce the ESR base value. But still far from satisfying the design of high frequency circuit, taking tantalum electrolytic capacitor with capacity of 100 muF as an example, the equivalent series resistance ESR of the capacitor obtained by the method is 0.25 omega at high frequency of 100KHz, and the design requirement is below 0.075 omega, the reason of high ESR is that manganese dioxide MNO which is produced by the traditional process and plays the role of cathode2Has a large resistivity, and an oxide film Ta pentoxide as a dielectric layer formed on the surface of the anode compact2O5Manganese dioxide MNO forming cathode with its surface2The contact resistance between the layers is also large.
The invention content is as follows: the invention aims to solve the problems that manganese nitrate is decomposed at high temperature to obtain manganese dioxide with low resistivity (high conductivity) by changing the original cathode manufacturing process, and an oxide film serving as a dielectric layer of an electrolytic capacitor and MNO (manganese oxide) which is formed on the surface of the oxide film and plays a role of a cathode are formed2The contact resistance between layers is large. The conventional cathode manufacturing technique is to immerse an anode block having an oxide film in a manganese nitrate solution to allow the manganese nitrate solution to penetrate into the inside of the anode block, and then to feed the anode block at a high temperatureAnd decomposing the manganese nitrate repeatedly, wherein the concentration of the manganese nitrate solution is increased by 20 percent and 40 percent … 80 percent each time, so that a layer of manganese dioxide with a certain thickness is obtained inside and on the surface of the anode block.
The cathode manufacturing technology of the invention improves the wettability on the surface of a dielectric oxide film by doping manganese nitrate solution, so that manganese nitrate is decomposed at high temperature to obtain manganese dioxide MNO with low resistance (high conductivity)2Finally, the equivalent series resistance ESR of the capacitor at high frequency is greatly reduced.
The production of the solid electrolytic capacitor cathode comprises two parts of a process flow and a processing process condition.
The process flow is as shown in the attached figure of the specification.
As can be seen from the figure, the process flow of the invention comprises the following steps in sequence:
the first step is as follows: immersing the anode billet with the oxide film into a dilute manganese nitrate solution containing ethanol for immersion, then taking out the billet and putting the billet into decomposition equipment with water vapor and oxygen for heating and decomposition, and repeating the steps for a plurality of times;
a second step; immersing the anode briquettes treated in the first step into a concentrated manganese nitrate solution containing ammonium nitrate for impregnation, taking out the briquettes, putting the briquettes into decomposition equipment filled with water vapor and oxygen, and heating and decomposing for a plurality of times;
the third step: immersing the anode briquette treated in the second step into a manganese nitrate solution containing suspended manganese dioxide for impregnation, taking out the briquette, and putting the briquette into a decomposition device filled with water vapor and oxygen for heating and decomposition for one time;
the fourth step: immersing the anode briquettes treated in the third step into a dilute manganese nitrate solution containing ammonium nitrate for impregnation, taking out the briquettes, and putting the briquettes into decomposition equipment filled with water vapor and oxygen for heating and decomposition;
and the post-processing process and the process conditions of the anode billet processed in the fourth step are the same as those of the traditional process, namely, the anode billet processed in the thermal decomposition process is soaked into a dilute acetic acid solution for being supplemented for 4-5 times, then graphite with the mass concentration of 2-8% is soaked, then the anode billet is dried, finally a silver paste layer is coated on the lead frame, and the anode billet is packaged in a metal shell through resin mould pressing or coated with the silver paste layer.
The specific steps and general process conditions of the production processing technology are as follows:
the first step is as follows: immersing the anode billet with the oxide film into a dilute manganese nitrate solution containing absolute ethyl alcohol, wherein the specific gravity d of the manganese nitrate solution containing absolute ethyl alcohol is 1.10g/cm3～1.30g/cm3The mass percent of the absolute ethyl alcohol in the solution is 0.5-15%, the absolute ethyl alcohol is used as a penetrating agent, the dipping time in the solution is 5-12 minutes, and the anode billet is taken out after dipping and placed in a decomposing device for heating and decomposing;
the decomposition time is 2-15 minutes, the decomposition temperature is 200-330 ℃, water vapor and oxygen are introduced into the decomposition equipment, the water vapor pressure is 0.03-0.1 Mpa, the oxygen mass percentage concentration is 9-14%, and the steps are repeated for 4-10 times;
the second step is that: immersing the anode compact treated in the first step into a concentrated manganese nitrate solution containing ammonium nitrate, NH4NO3The specific gravity d of the manganese nitrate solution is 1.55g/cm3～1.85g/cm3And taking out the anode billet after impregnation, placing the anode billet in a decomposition device for heating decomposition, wherein the mass percent of ammonium nitrate in the solution is 0.1-40%, the ammonium nitrate is used as a catalyst, the impregnation time in the solution is 3-10 minutes:
the decomposition time is 4-12 minutes, the decomposition temperature is 200-250 ℃, water vapor and oxygen are introduced into the decomposition equipment, the water vapor pressure is 0.03-0.1 Mpa, the oxygen mass percentageconcentration is 9-14%, and the steps are repeated for 2-6 times;
thirdly, dipping the anode billet treated in the second step into MNO containing solid manganese dioxide2The specific gravity d of the manganese nitrate solution containing solid manganese dioxide is 1.7g/cm3～2.5g/cm3The mass percent of manganese dioxide in the solution is 40%, the dipping time in the solution is 3-12 minutes, the anode billet block is taken out after dipping and placed in a decomposition device for heating decomposition, the decomposition time is 4-12 minutes, the decomposition temperature is 180-250 ℃, water vapor and oxygen are introduced into the decomposition device, the water vapor pressure is 0.03-0.1 Mpa, the mass percent concentration of the oxygen is 9-14%, and the treatment times are 1 time;
fourthly, immersing the anode compact treated in the third step into a dilute manganese nitrate solution containing ammonium nitrate, wherein the specific gravity d of the manganese nitrate solution containing ammonium nitrate is 1.10g/cm3～1.55g/cm3The mass percentage of ammonium nitrate in the solution is5 percent, the dipping time is 3-10 minutes, the anode billet block is taken out after dipping and placed in a decomposition device for heating decomposition, the decomposition time is 4-12 minutes, the decomposition temperature is 180-250 ℃, water vapor and oxygen are introduced into the decomposition device, the water vapor pressure is 0.03-0.1 Mpa, the oxygen mass percent is 9-14 percent, and the treatment times are 1 time.
The post-processing procedure and process conditions of the anode compact after the fourth step are the same as those of the conventional process, see specification of patent application No. 200410079295.2.
Although the aforesaid process flow and process conditions can greatly reduce the ESR value of the conventional process, the ESR value can be further reduced by strictly controlling the processing process conditions, which include:
the first step is as follows: the specific gravity d of the manganese nitrate solution containing absolute ethyl alcohol is 1.12g/cm3～1.18g/cm3The mass percentage of absolute ethyl alcohol in the manganese nitrate solution is 2-8%, and the dipping time in the solution is 6-8%The decomposition temperature is 200-280 ℃, the decomposition time is 5-7 minutes, the water vapor pressure in the decomposition equipment is 0.03-0.0 gMpa, and the oxygen mass percentage concentration is 10-13%; the second step is that: the specific gravity d of manganese nitrate solution containing ammonium nitrate is 1.60g/cm3～1.7gg/cm32-5% of ammonium nitrate in the solution by mass, 5-7 min of soaking in the solution, 200-250 ℃ of decomposition temperature, 6-8 min of decomposition time, 0.03-0.08 Mpa of water vapor pressure in the decomposition equipment and 9-13% of oxygen mass concentration;
the third step: specific gravity d of manganese nitrate solution containing solid manganese dioxide is 1.7g/cm3～2.5g/cm3The mass percent of manganese dioxide in the solution is 40%, the dipping time is 3-12 minutes, the decomposition temperature is 180-250 ℃, the decomposition time is 4-8 minutes, the vapor pressure of water in the decomposition equipment is 0.03-0.0 gMpa, and the mass percent concentration of oxygen is 10-13%;
the fourth step: the specific gravity d of dilute manganese nitrate solution containing ammonium nitrate is 1.30g/cm3～1.55g/cm35 percent of ammonium nitrate in the solution by mass, 3 to 10 minutes of dipping time in the solution, 180 to 250 ℃ of decomposition temperature, 4 to 8 minutes of decomposition time, 0.03 to 0.06Mpa of water vapor pressure in the decomposition equipment and concentrated oxygen by massThe degree is 10-13%.
All the percentage concentrations of the invention are calculated by mass percentage.
Example 1: the first step is as follows: selecting 1000 tantalum briquettes with the size of 1.6 multiplied by 3.3 multiplied by 4.3(mm) to prepare a tantalum capacitor with the size of 16v and 100 mu F, and after vacuum sintering, applying energizing voltage of 45-60 v to the tantalum briquettes in phosphoric acid solution with the mass concentration of 0.01-0.1% to generate an oxide film Ta2O5Then adding 5% by weight of absolute ethyl alcohol, and respectively setting the specific gravity d to 1.12g/cm3，d＝1.18g/cm3Dipping in the dilute manganese nitrate solution for 8 minutes, then thermally decomposing for 7 minutes under the conditions that the temperature is 250 ℃, the oxygen mass percentage content is 11.5-12% and the water vapor pressure is 0.0gMpa, and repeating the steps for 4-10 times; the second step is that: first step ofThe specific gravity d of the finished briquette added with ammonium nitrate with the mass percentage concentration of 4 percent is 1.65g/cm3～1.75g/cm3Dipping the manganese nitrate solution for 6 minutes, then heating and decomposing the manganese nitrate solution for 6 minutes under the conditions that the temperature is 210 ℃, the oxygen mass percentage content is 12-13 percent and the water vapor pressure is 0.06Mpa, and repeating the steps for 2-6 times; the third step: immersing the blank block after the second step into a manganese nitrate solution containing 40 percent of solid manganese dioxide by mass percent, wherein the specific gravity d of the manganese nitrate solution is 1.7g/cm3～2.5g/cm3Dipping for 3-12 minutes, dehydrating and drying to form a strengthening layer, and then heating and decomposingunder the same condition as the second step; the fourth step: immersing the compact after the third step into a mixture containing 5 percent of ammonium nitrate and having a specific gravity d of 1.5g/cm3The diluted manganese nitrate solution is soaked for 3-10 minutes, and then is heated and decomposed for 6 minutes under the conditions that the temperature is 210 ℃, the oxygen mass percentage content is 12-13%, and the water vapor pressure is 0.03Mpa, so that the damage of an oxidation film in the thermal decomposition is repaired, and after the thermal decomposition process, the diluted manganese nitrate solution is formed for 4-5 times in a glacial acetic acid solution with the concentration of 0.01%. And after the completion, immersing the graphite with the solid content of 1.5-6% into the graphite, drying the graphite, finally coating a silver paste layer, installing the silver paste layer on a lead frame, and carrying out resin mould pressing and packaging. The ESR value of the product is in the range of 0.05-0.09 omega by 100KHz measurement.
Example 2: 1000 pieces of tantalum blocks having a block size of 1.6X 3.3X 4.3(mm) were selected to prepare a tantalum capacitor of 10 v-220. mu.F, and a manganese dioxide, graphite, silver paste cathode layer was formed on the surface of the anode tantalum block in the same manner as in example 1. And then the tantalum capacitor is manufactured after being arranged on a lead frame and molded by resin, and the ESR value of the tantalum capacitor is in the range of 0.04-0.08 omega when the ESR value is measured by 100 KHz.
Example 3: a tantalum capacitor of 16v-100 μ F was prepared from 1000 pieces of tantalum having a billet size of 1.6X 3.3X 4.3(mm), and the diluted manganese nitrate was decomposed at 280 ℃ and the specific gravity d was 1.65g/cm (in comparison with example 1)3～1.75g/cm3The decomposition temperature of the concentrated manganese nitrate is 240℃,other conditions are the same) has an ESR value in the range of 0.05-0.08 omega when measured by 100 KHz.
Example 4: a tantalum capacitor of 20v68 μ F was prepared from 1000 pieces of tantalum having a billet size of 2.8X 3.3X 4.3(mm), and the ESR value of the tantalum capacitor prepared by the method of example 1 was in the range of 0.06-0.10. omega. when measured at 100 KHZ.
Example 5: a50 v4.7 μ F tantalum capacitor was prepared from 1000 pieces of tantalum having a billet size of 1.6X 3.3X 4.3(mm) by the same method as in example 3, and the ESR value was in the range of 0.18 to 0.24. omega. when measured at 100 KHZ.
Example 6: a tantalum block having a size of 1.6X 3.3X 4.3(mm) was selected to prepare a tantalum capacitor of 10v 220. mu.F, and the tantalum capacitor was prepared by the same method as in example 3, and its ESR value was in the range of 0.05 to 0.07. omega. as measured under the condition of 100 KHz.
Example 7: the tantalum briquettes from example 1 to example 6 were processed using the widest range of process conditions of the present invention (i.e., the general process conditions described in the specification), and the results are shown in table 1.
Example 8: a tantalum block having a block size of 6.5X 5(mm) was selected to prepare a 20v47 μ F tantalum capacitor, and the same procedure as in example 1 was used to prepare a capacitor having MnO2Tantalum block of the layer, MnO after completion2The surface of the layer is coated with a graphite layer and a silver paste layer, and finally the graphite layer and the silver paste layer are encapsulated in a cylindrical metal shell with the diameter of 8 multiplied by 14(mm) by using soldering tin. The ESR value of the product is in the range of 0.06-0.08 omega by 100KHz measurement.
The capacitor with capacity of 100 μ F produced according to the process has equivalent series resistance value of 0.075 or less measured at high frequency of 100KHz, which is about one third of that produced under conventional process conditions, and the manganese dioxide layer and dielectric oxide film Ta of the capacitor produced by the process2O5The contact resistance between the graphite layer and the silver layer is very small, the contact area between the manganese dioxide and the graphite layer and between the manganese dioxide and the silver layer is increased, the contact resistance is reduced, and the capacitance is greatly reducedAnd the equivalent series resistance ESR value of the capacitor is increased, and the damage resistance of the capacitor in a mechanical test is improved.
The ESR values of the electrolytic capacitors produced by the present invention will now be compared with those of the electrolytic capacitors produced by the conventional processes. The results are shown in Table 1
TABLE 1 comparison of 100KHz measured ESR values for products of the inventive and conventional processes
As can be seen from the table, the ESR values can be greatly reduced according to the process flow and general process conditions of the present invention, and products with lower ESR can be produced if the process conditions are strictly controlled.
Claims (4)
1. A method for manufacturing a cathode of a solid electrolytic capacitor comprises the steps of coating a graphite layer and a silver layer on a manganese dioxide surface layer, and carrying out resin mould pressing packaging in a metal shell or on a lead frame, and is characterized in that the method sequentially comprises the following steps: the first step is as follows: immersing the anode billet with the oxide film into a dilute manganese nitrate solution containing ethanol for immersion, then taking out the billet and putting the billet into decomposition equipment filled with water vapor and oxygen for heating decomposition, and repeating the steps for a plurality of times;
the second step is that: immersing the anode briquettes treated in the first step into a concentrated manganese nitrate solution containing ammonium nitrate for impregnation, taking out the briquettes, putting the briquettes into decomposition equipment filled with water vapor and oxygen, and heating and decomposing for a plurality of times;
the third step: immersing the anode briquette treated in the second step into a manganese nitrate solution containing suspended manganese dioxide for impregnation, taking out the briquette, and putting the briquette into a decomposition device filled with water vapor and oxygen for heating and decomposition for one time;
the fourth step: and (3) immersing the anode briquettes treated in the third step into a dilute manganese nitrate solution containing ammonium nitrate for immersion, taking out the briquettes, and putting the briquettes into decomposition equipment filled with water vapor for heating and decomposition.
2. The method for producing a cathode for a solid electrolytic capacitor as claimed in claim 1, wherein the process conditions in the respective steps are as follows: the first step is as follows: the specific gravity d of the manganese nitrate solution containing absolute ethyl alcohol is 1.10g/cm3～1.3g/cm3The manganese nitrate solution contains 0.5-15% of absolute ethyl alcohol by mass, the dipping time in the solution is 5-12 minutes, the decomposition temperature is 200-330 ℃, the decomposition time is 2-15 minutes, the water vapor pressure is 0.03-0.1 Mpa, and the oxygen mass percentage concentration is 9-14%; the second step is that: the specific gravity d of the manganese nitrate solution containing ammonium nitrate is 1.55g/cm3～1.85g/cm3The mass percent of ammonium nitrate in the solution is 0.1-40%, and the dipping time in the solution is 3-cThe decomposition temperature is 200-250 ℃, the decomposition time is 4-12 minutes, the water vapor pressure is 0.03-0.1 Mpa, and the oxygen mass percentage concentration is 9-14%;
the third step: manganese nitrate solution containing round manganese dioxide with specific gravity d of 1.7g/cm3～2.5g/cm3The mass percent of manganese dioxide in the solution is 40%, the dipping time is 3-12 minutes, the decomposition temperature is 180-250 ℃, the decomposition time is 4-12 minutes, the water vapor pressure is 0.03-0.1 Mpa, and the oxygen mass percent concentration is 9-14%;
the fourth step: containing NH4NO3The specific gravity d of the dilute manganese nitrate solution is 1.10g/cm3～1.55g/cm3The mass percent of ammonium nitrate in the solution is 5%, the dipping time is 3-10 minutes, the decomposition temperature is 180-250 ℃, the decomposition time is 4-12 minutes, the water vapor pressure is 0.03-0.1 Mpa, and the oxygen mass percent concentration is 9-14%.
3. The method for producing a cathode for a solid electrolytic capacitor as claimed in claim 1The method is characterized in that the process conditions of the steps are as follows: the first step is as follows: the specific gravity d of the manganese nitrate solution containing absolute ethyl alcohol is 1.12g/cm3～1.18g/cm3The manganese nitrate solution contains 2-8% of absolute ethyl alcohol by mass, the dipping time in the solution is 6-8 minutes, the decomposition temperature is 200-280 ℃, the decomposition time is 6-8 minutes, the water vapor pressure in the decomposition equipment is 0.03-0.1 Mpa, and the oxygen mass percentage concentration is 10-13%; the second step is that: the specific gravity d of manganese nitrate solution containing ammonium nitrate is 1.60g/cm3～1.78g/cm32-5% of ammonium nitrate in the solution by mass, 5-7 min of soaking in the solution, 200-250 ℃ of decomposition temperature, 6-8 min of decomposition time, 0.03-0.08 Mpa of water vapor pressure in the decomposition equipment and 9-13% of oxygen mass concentration;
the third step: specific gravity d of manganese nitrate solution containing solid manganese dioxide is 1.7g/cm3～2.5g/cm3The mass percent of manganese dioxide in the solution is 40%, the dipping time is 3-12 minutes, the decomposition temperature is 180-250 ℃, the decomposition time is 4-8 minutes, and water in the decomposition equipmentThe steam pressure is 0.03-0.08 Mpa, and the oxygen mass percentage concentration is 10-13%;
the fourth step: the specific gravity d of dilute manganese nitrate solution containing ammonium nitrate is 1.30g/cm3～1.55g/cm35% of ammonium nitrate in the solution by mass, 3-10 min of dipping time in the solution, 180-250 ℃ of decomposition temperature, 4-8 min of decomposition time, 0.03-0.06 Mpa of water vapor pressure in the decomposition equipment and 10-13% of oxygen mass concentration.
4. The method for producing a cathode for a solid electrolytic capacitor as claimed in claim 1, wherein the process conditions in the respective steps are as follows: the first step is as follows: the specific gravity d of the manganese nitrate solution containing absolute ethyl alcohol is 1.12g/cm3～1.18g/cm35% of absolute ethyl alcohol in the manganese nitrate solution by mass, 8 minutes of soaking time, 250 ℃ of decomposition temperature, 7 minutes of decomposition time, 0.08Mpa of water vapor pressure and 11-12% of oxygen by mass; the second step is that: the specific gravity d of manganese nitrate solution containing ammonium nitrate is 1.65g/cm3～1.75g/cm34% by mass of ammonium nitrate and 6% by mass of dipping timeThe decomposition temperature is 210 ℃, the decomposition time is 6 minutes, the water vapor pressure is 0.061Mpa, and the oxygen mass percentage concentration is 12-13%;
the third step: specific gravity d of manganese nitrate solution containing solid manganese dioxide is 1.65g/cm3～1.75g/cm340% of manganese dioxide in a manganese nitrate solution, 6 minutes of soaking time, 210 ℃ of decomposition temperature, 6 minutes of decomposition time, 0.06MPa of water vapor pressure and 12-13% of oxygen mass percentage concentration;
the fourth step: containing NH4NO3The specific gravity d of the dilute manganese nitrate solution is 1.5g/cm35 mass percent of ammonium nitrate in the manganese nitrate solution, 6 minutes of soaking time, 210 ℃ of decomposition temperature, 6 minutes of decomposition time, 0.03MPa of water vapor pressure and 12-13 mass percent of oxygen.
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| CN101681724B (en) * | 2007-05-21 | 2012-01-18 | 昭和电工株式会社 | Method and apparatus for manufacturing solid electrolytic capacitor |
| CN102751102A (en) * | 2012-07-18 | 2012-10-24 | 中国振华（集团）新云电子元器件有限责任公司 | Method for reducing equivalent series resistance of electrolytic capacitor |
| CN102800480A (en) * | 2012-08-24 | 2012-11-28 | 中国振华（集团）新云电子元器件有限责任公司 | Preparation method for cathode of Nb capacitor |
| CN102842434A (en) * | 2012-09-06 | 2012-12-26 | 深圳顺络电子股份有限公司 | Preparation method for cathode of electrolytic capacitor |
| CN103366963A (en) * | 2013-07-22 | 2013-10-23 | 株洲宏达电子有限公司 | High-temperature sheet-type tantalum capacitor and manufacturing method thereof |
| CN104538181A (en) * | 2014-12-29 | 2015-04-22 | 中国振华（集团）新云电子元器件有限责任公司 | Compacting method for manganese dioxide layer forming of tantalum capacitor |
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| CN101681724B (en) * | 2007-05-21 | 2012-01-18 | 昭和电工株式会社 | Method and apparatus for manufacturing solid electrolytic capacitor |
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| CN102800480B (en) * | 2012-08-24 | 2016-01-13 | 中国振华（集团）新云电子元器件有限责任公司 | A kind of preparation method for cathode of Nb capacitor |
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| CN102842434A (en) * | 2012-09-06 | 2012-12-26 | 深圳顺络电子股份有限公司 | Preparation method for cathode of electrolytic capacitor |
| CN103366963A (en) * | 2013-07-22 | 2013-10-23 | 株洲宏达电子有限公司 | High-temperature sheet-type tantalum capacitor and manufacturing method thereof |
| CN103366963B (en) * | 2013-07-22 | 2016-05-18 | 株洲宏达电子股份有限公司 | High temperature chip tantalum capacitor and preparation method thereof |
| CN104538181A (en) * | 2014-12-29 | 2015-04-22 | 中国振华（集团）新云电子元器件有限责任公司 | Compacting method for manganese dioxide layer forming of tantalum capacitor |
| CN104538181B (en) * | 2014-12-29 | 2017-06-16 | 中国振华（集团）新云电子元器件有限责任公司 | A kind of dense method of tantalum capacitor envelope |
| CN108133826A (en) * | 2017-12-21 | 2018-06-08 | 中国振华（集团）新云电子元器件有限责任公司 | A kind of raising tantalum capacitor is by the method for membrane capacity |
| CN112038093A (en) * | 2020-09-23 | 2020-12-04 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Tantalum capacitor solid electrolyte and preparation method thereof, tantalum capacitor and electrical appliance |
| CN112038093B (en) * | 2020-09-23 | 2022-07-26 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Tantalum capacitor solid electrolyte and preparation method thereof, tantalum capacitor and electrical appliance |
| CN116206902A (en) * | 2023-04-14 | 2023-06-02 | 福建火炬电子科技股份有限公司 | Manganese dioxide cathode of welding-resistant tantalum electrolytic capacitor, capacitor and preparation method of manganese dioxide cathode |
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