Electrolytic capacitors based on n-type conductive polymers and their manufacturing process.

Abstract

The present invention provides an electrolytic capacitor based on an n-type conductive polymer and a manufacturing process for the same. The capacitor comprises a wound body formed by laminating a negative electrode foil, electrolytic paper, and a positive electrode foil with an oxide film dielectric formed on its surface in this order and winding them together. The wound body has an n-type conductive polymer electrolyte layer inside, and the material of the n-type conductive polymer electrolyte layer contains one or more types of n-type conductive polymers, the n-type conductive polymer having repeating units of formula (I) which is a negatively charged conjugated structure as shown below, where X is one of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or a nitrogen atom, and when X is a nitrogen atom, R is one of a hydrogen atom, a linear alkyl, or an isoalkyl, and when X is one of an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, R is absent, and Y + represents a cation. The conjugated repeating units of the negatively charged structure may be the same or different. The resulting capacitor has low ESR and high stability. [Formula 1] TIFF2026519187000011.tif47169

Description

【Technical Field】 【0001】 The present invention relates to the technical field of capacitors, and specifically, to electrolytic capacitors based on n-type conductive polymers and their manufacturing processes. 【Background Art】 【0002】 Conductive polymer materials can be classified into two categories: intrinsic conductive polymer materials and composite conductive polymer materials according to their manufacturing methods and conductive mechanisms. Among them, intrinsic conductive polymer materials have a π-conjugated structure, which enables the carriers in the main chain to be sufficiently delocalized, resulting in conductivity. Conjugated polymers with a π-conjugated structure generally have a very low carrier concentration and exhibit semiconductor characteristics. Therefore, in order to increase the carrier concentration and create favorable conditions for the delocalization of electrons by changing the original energy band structure to obtain conductivity, an external action (such as doping) is required. Doping can be divided into p-type doping and n-type doping. P-type doping generally refers to the process of partially oxidizing the π-conjugated main chain of an organic conjugated polymer to endow it with freely movable cation carriers. This process was first discovered in trans-polyacetylene. By treating trans-polyacetylene with an oxidizing agent such as iodine, the conductivity of polyacetylene increases by more than seven orders of magnitude by delocalizing about 85% of the positive charge over more than 15 repeating units. Currently, various p-type conductive polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT), polyaniline (PANI), and polypyrrole (PPy) have been developed. 【0003】 Despite significant advances in the synthesis and preparation of conductive polymers, most doping methods still focus on p-type doping, resulting in doped conductive polymers exhibiting hole-dominant charge transport behavior. The development of n-type conductive polymers has lagged significantly, mainly due to low doping efficiency and poor stability. For example, lithium-doped n-type polyacetylenes exhibit much lower conductivity than iodine-doped p-type polyacetylenes, and also have difficulty maintaining stability in air. 【0004】 Currently, PEDOT is used as a conductive polymer in both solid-liquid mixed capacitors and solid lead electrolytic capacitors in the capacitor industry. PEDOT is a p-type doped conductive polymer material that conducts electricity via cation carriers (holes). Its characteristics in capacitor applications are as follows: (1) Because the main chain of PEDOT is positively charged, prolonged use as the negative electrode of a capacitor makes it susceptible to oxygen attack during the electron storage and output operation process, leading to dedoping problems, decreased conductivity, and capacitor failure. (2) The equivalent series resistance (ESR) of a capacitor depends heavily on the conductivity of the conductive polymer, and the upper limit of PEDOT conductivity is usually less than 500 S / cm. (3) The thermal decomposition temperature of currently synthesized PEDOT is generally below 200°C. If the thermal decomposition temperature is too low, it becomes difficult to use it as the working electrolyte in solid capacitors to operate in high-temperature environments above 150°C, which is a bottleneck in the research of high-temperature solid capacitors. Currently, there are very few solid capacitors on the market that operate at temperatures exceeding 150°C. (4) Since PEDOT is insoluble in solvents, in actual manufacturing it is necessary to disperse it in water using a dispersant to make a dispersion. However, the degree of dispersion is very low and it is prone to aggregation, so very precise timing is required for its use. [Overview of the Initiative] 【0005】 To address the technical challenges of existing p-type conductive polymer materials used in electrolytic capacitors, such as susceptibility to dedoping, low conductivity, poor thermal stability, and poor dispersibility of impregnation solutions, the present invention provides an electrolytic capacitor based on an n-type conductive polymer and a manufacturing process therefor. By combining an n-type conductive polymer with an improved process, it is possible to obtain a capacitor anode electrolyte with conductivity exceeding 500 S / cm, realizing an electrolytic capacitor with ultra-low ESR and ultra-high stability. [Modes for carrying out the invention] 【0006】 To achieve the above objectives, the present invention is realized by the following technical solutions. 【0007】 One aspect of the present invention is, An electrolytic capacitor based on an n-type conductive polymer, comprising a wound body formed by laminating and winding a negative electrode foil, electrolytic paper, and a positive electrode foil with an oxide film dielectric formed on its surface in this order, The coiled body has an n-type conductive polymer electrolyte layer inside, The present invention provides an electrolytic capacitor characterized in that the material of the n-type conductive polymer electrolyte layer contains one or more types of n-type conductive polymers, and the n-type conductive polymers contain repeating units of the following negatively charged conjugated structure. 【0008】 [ka] (Here, X is one of the following: oxygen atom, sulfur atom, selenium atom, tellurium atom, nitrogen atom. If X is a nitrogen atom, R is one of the following: hydrogen atom, linear alkyl, isoalkyl. If X is one of the following: oxygen atom, sulfur atom, selenium atom, tellurium atom, R is absent, Y + (The cations represent cations, and the repeating units of the negatively charged conjugated structure are either identical or different.) 【0009】 Furthermore, the conductivity of the n-type conductive polymer is 500 S / cm to 8000 S / cm, and the molecular weight of the n-type conductive polymer is at least 1 kDa, preferably 100 kDa to 5000 kDa. A cation is one or more selected from hydrogen ions, ammonium ions, pyridinium salt ions, and metal ions. 【0010】 Furthermore, the weight ratio of the n-type conductive polymer electrolyte layer in the wound material is at least 1%. 【0011】 Furthermore, the electrolytic capacitor includes an electrolyte in which the wound body is immersed, a case that houses the wound body and the electrolyte, and a sealing member that seals the case. The electrolyte contains, as its components, a solvent, a solute, and additives. The solvent is selected from either an aprotic polar solvent or a protic polar solvent. The aprotic polar solvent is one or more selected from γ-butyrolactone (GBL), sulfolane (SFL), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), and N-methylformamide (NMF). The protic polar solvent is one or more selected from ethylene glycol, glycerol, diglycol, triglycol, polyglycerol, polyglycerol ether, and polyols containing multiple hydroxyls. The solute is one or more of the following: organic acids, inorganic acids, and organic alkalis. The organic acid is one or more selected from phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, benzoic acid, malonic acid, succinic acid, and disalicylic boride. The organic alkali is selected from organic amines and / or imidazoline compounds. The organic amines include primary, secondary, and tertiary amines. Primary amines are selected from methylamine, ethylamine, propylamine, etc. Secondary amines are selected from dimethylamine, diethylamine, ethylmethylamine, dibutylamine, diisopropylamine, etc. Tertiary amines are selected from trimethylamine, triethylamine, tributylamine, ethyldiisopropylamine, etc. Imidazolins are selected from ethyldimethylimidazoline, 1,2,3,4-tetramethylimidazoline, etc. The additives are selected from nitro compounds such as p-nitrobenzoic acid, m-nitroacetophenone, and p-nitrobenzyl alcohol. 【0012】 Furthermore, the case is made of metal. Electrolytic paper is selected from synthetic fibers and / or natural fibers. Synthetic fibers include, for example, polyester fibers, polyamide fibers, polypropylene fibers, aramid fibers, cellulose fibers (e.g., viscose fibers, acetate fibers, cupro fibers, etc.), while natural fibers include, for example, Manila hemp, esparto, cotton fibers, etc. The positive and negative electrode foils are each made of lead valve metal, and each of the positive and negative electrode foils further has a lead pin. 【0013】 Another aspect of the present invention is, Step (1) involves winding the positive electrode foil, electrolytic paper, and negative electrode foil in this order to form a first winding of a desired specification, and subjecting the first winding to at least one formation process, which includes forming and drying, to obtain a second winding. Step (2) is to form an electrolyte layer having an n-type conductive polymer inside the second wound body to obtain a third wound body, The present invention provides a manufacturing process for an electrolytic capacitor based on an n-type conductive polymer, comprising the steps of (3) placing the capacitor in a case, sealing it, and aging it by applying current to obtain an electrolytic capacitor based on an n-type conductive polymer. 【0014】 Furthermore, in step (2), the step of forming an electrolyte layer having an n-type conductive polymer is to immerse the second coil in an n-type conductive polymer solution and perform an impregnation treatment at least once, the impregnation treatment including impregnation followed by drying, and the n-type conductive polymer solution contains one or more types of n-type conductive polymers. 【0015】 Furthermore, the n-type conductive polymer solution contains 0.1 wt% to 10 wt% of the n-type conductive polymer, and the remaining amount of organic solvent to replenish it up to 100 wt%. The organic solvent is one or more selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, amines, esters, ethers, ketones, dimethyl sulfoxides, amides (e.g., N,N-dimethylformamide, N-methylformamide, etc.), and sulfolanes. It should be noted that amines and amides are not the same type of substance, and amines include, for example, primary amines, secondary amines, and tertiary amines. Preferably, the n-type conductive polymer solution contains 0.5 wt% to 3 wt% of the n-type conductive polymer and the remainder of the organic solvent to replenish up to 100 wt%. 【0016】 Furthermore, in step (2), the step of forming an electrolyte layer having an n-type conductive polymer involves performing the steps of impregnation with an n-type conductive polymer monomer solution, drying, impregnation with an oxidizing agent solution, and drying on the second wound body at least once in this order by a stepwise impregnation method to obtain a third wound body, wherein the n-type conductive polymer monomer solution contains one or more types of n-type conductive polymer monomers. Alternatively, in step (2), the step of forming an electrolyte layer having an n-type conductive polymer involves dropping a mixed solution containing both one or more n-type conductive polymer monomers and an oxidizing agent onto the second wound body at least once by a dropwise method, then performing thermal polymerization at least once, and then drying to obtain a third wound body. n-type conductive polymer monomers have the following structure. 【0017】 【Chem.】 (Here, X is one of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and a nitrogen atom. When X is a nitrogen atom, R is one of a hydrogen atom, a linear alkyl, and an isoalkyl. When X is one of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom, R does not exist.). 【0018】 Further, in step (2) adopting a stepwise impregnation method, the n-type conductive polymer monomer solution contains 0.1 wt% to 5 wt% of an n-type conductive polymer monomer and a residual amount of an organic solvent supplemented up to 100 wt%, In step (2) adopting a dropping method, the thermal polymerization is carried out at 50 °C to 150 °C under nitrogen protection. Preferably, the temperature of the thermal polymerization is 70 to 120 °C, more preferably 80 to 100 °C, and most preferably 80 °C. Here, the mixed solution containing both one or more n-type conductive polymer monomers and an oxidizing agent contains an n-type conductive polymer monomer, an oxidizing agent, and an organic solvent. The mass concentration of the n-type conductive polymer monomer is 1 wt% to 5 wt%, and the mass concentration of the oxidizing agent is 1 wt% to 5 wt%, The oxidizing agent solution contains 0.1 wt% to 10 wt% of an oxidizing agent and a residual amount of an organic solvent supplemented up to 100 wt%. The oxidizing agent is one or more selected from oxygen gas, peroxides, metal salts, persulfates, perborates, hypohalites, quinone-based compounds, and perbenzoic acids. The organic solvent is one or more selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, amines, esters, ethers, ketones, dimethyl sulfoxide, amides, and sulfolane. 【0019】 Moreover, in step (2) of adopting a stepwise impregnation method, after the steps of impregnation with an oxidizing agent solution and drying, it further includes a step of impregnation with an additive compound solution. The additive compound solution contains 1 wt% to 5 wt% of the additive compound and the remaining amount of organic solvent replenished up to 100 wt%. In step (2) of adopting a dropping method, the mixed solution further contains an additive compound, and the mass concentration of the additive compound in the mixed solution is 1 wt% to 5 wt%. The additive compound includes one or more of pyridine-based compounds and quaternary ammonium-based compounds. 【0020】 Furthermore, in step (2), pressure impregnation or vacuum negative pressure impregnation is adopted as the impregnation. In step (2), the drying is carried out at a temperature of 80°C to 150°C for a time of 5 minutes to 300 minutes. 【0021】 Furthermore, in step (1), the drying is carried out at a temperature of 80°C to 150°C for a time of 5 minutes to 300 minutes. Before forming the first wound body, the lead pins are respectively crimped to the positive electrode foil and the negative electrode foil. In step (1), the formation is to immerse the first wound body in the formation solution, and then apply the formation voltage same as the voltage of the anode foil of the first wound body. The formation solution is used to repair the dielectric oxide film or form a new dielectric oxide film. As the formation solution, one or more of ammonium dihydrogen phosphate aqueous solution, ammonium borate aqueous solution, boric acid aqueous solution, and ammonium adipate aqueous solution may be used. 【0022】 Furthermore, step (3) further includes impregnating the third wound body with the electrolytic solution and impregnating the third wound body in the electrolytic solution for 5 minutes to 10 minutes using a relative negative pressure of -90 Kpa. In step (3), when the electrolytic solution is adopted, the electrolytic capacitor becomes a solid-liquid mixed electrolytic capacitor. Otherwise, the electrolytic capacitor is a solid electrolytic capacitor. 【0023】 The beneficial technical effects are as follows: 【0024】 The solutions of the present invention include solid capacitors and solid-liquid mixed capacitors. The differences from conventional capacitors are as follows: The present invention uses an n-type conductive polymer as the electrolyte of the capacitor. The n-type conductive polymer used has excellent solution processability and can be prepared in solutions of various concentrations, thus having high manufacturing adaptability and functioning as the negative electrode of the capacitor. The main chain of the n-type conductive polymer used is negatively charged, further improving its compatibility with the negative electrode of the capacitor. Furthermore, the n-type conductive polymer has an conductivity of 500 S / cm to 8000 S / cm and conducts electricity via electrons as the negative electrode of the capacitor, thus enabling the capacitor to have higher capacitance and lower ESR. In addition, the n-type conductive polymer used has high thermal stability in air, is less prone to dedoping reactions, and is less likely to decompose even at high temperatures. Capacitors manufactured therein can maintain high capacitance and low ESR even after 4000 hours of operation under double 85 conditions, demonstrating good stability. [Examples] 【0025】 The following description will clearly and completely explain the technical solutions in embodiments of the present invention with reference to examples of the present invention, although it is clear that the examples described are only a part of the embodiments of the present invention and not all embodiments. The description of at least one exemplary embodiment below is, in fact, merely descriptive and does not limit the present invention or its application or use in any way. All other embodiments obtained by those skilled in the art without creative work based on embodiments of the present invention are within the scope of the protection of the present invention. 【0026】 The numerical values ​​described in these examples do not limit the scope of the invention unless otherwise specifically stated. Techniques and methods known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques and methods should be considered part of the specification. In all examples shown and discussed herein, any specific values ​​should be construed as merely illustrative and not limiting. Accordingly, other examples of the exemplary embodiments may have different values. 【0027】 Furthermore, the use of terms such as "first," "second," etc., to describe the wound bodies is merely to facilitate the distinction of the wound bodies in each manufacturing step, and unless otherwise specified, these terms do not have any special meaning and should not be understood as limiting the scope of protection of the present invention. 【0028】 In the following examples, experimental methods for which no specific conditions are specified are generally measured according to national standards, and if there is no corresponding national standard, they are measured according to general international standards or standards proposed by the relevant companies. Unless otherwise specified, all parts are parts by weight, and all percentages are weight percentages. 【0029】 The raw material 3,7-dihydrobenzo[1,2-b:4,5-b']dithiophene-2,6-dione used in the following examples is prepared according to the methods disclosed in the literature Chemistry Letters, 1983, 905-908 and Organic Electronics, 2016, 35, 41-46, and the CAS number of the raw material 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione used is 30272-74-3. 【0030】 Example 1 Electrolytic capacitor based on n-type conductive polymer: In this embodiment, a 16V 470μF 6.3×11 solid capacitor was manufactured by impregnating an n-type conductive polymer with a DMSO solution. The manufacturing process of the solid capacitor includes the following steps. 【0031】 (1) The positive electrode foil, electrolytic paper, and negative electrode were each cut to the required width, and the positive electrode foil, electrolytic paper, and negative electrode foil were wound in this order to form a first wound body of the desired specifications. The first wound body was butt-welded to a stainless steel bar, and then subjected to a formation treatment by placing it in a formation solution. After removal, it was dried, and the above "formation treatment and drying treatment" process was repeated twice to obtain a second wound body. Here, the formation treatment involves immersing the first wound body in a formation solution and then applying a formation voltage of 25VF. The formation solution is used to repair the dielectric lead oxide film or to form a new dielectric lead oxide film. In this example, the formation solution is an 8% by mass aqueous solution of ammonium adipate. 【0032】 (2) The second coiled body was placed in an n-type conductive polymer solution and pressurized using a hydraulic impregnation device at a pressure of 0.8 MPa at room temperature for 10 minutes. Then, it was vacuum-dried at 80°C for 150 minutes. The above "pressure impregnation and vacuum drying" step was repeated twice to obtain the third coiled body. 【0033】 The n-type conductive polymer solution was prepared by the following method: 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione (1 mmol) and the oxidizing agent duloquinone (1.5 mmol) were dissolved in 10 mL of dimethyl sulfoxide (DMSO). After vacuum degassing, the mixture was reacted at a relative negative pressure of -0.08 MPa and 80°C with stirring for 8 hours. The system was then diluted with DMSO to a solid content of approximately 15 mg / mL, and dialyzed in the DMSO solution using a dialysis bag (cutoff molecular weight = 10 kDa). The solution remaining in the dialysis bag was the n-type conductive polymer solution (where the concentration of n-type conductive polymer I is 1 wt%, and the remainder is DMSO). The related reactions are as follows. 【0034】 [ka] 【0035】 The n-type conductive polymer I obtained by the above reaction has a number-average molecular weight of M n The current is 323 kDa, the coefficient of dispersion is 2.41, the average conductivity is 6400 S / cm, in the structural formula m is 0.7 to 0.9 n, and the hydrogen ions are due to hydrogen removed from the raw material itself and water in the solvent or environment. 【0036】 (3) The third coil was fixed inside the lead case, assembled, and sealed to obtain a semi-finished capacitor. By charging and aging semi-finished capacitors, we obtained finished solid capacitors. The performance of the solid capacitor obtained in this embodiment was tested, and the detailed test results are shown in Table 1. 【0037】 Example 2 Electrolytic capacitor based on n-type conductive polymer: In this embodiment, a 16V 470μF 6.3×11 solid capacitor was manufactured by impregnating an n-type conductive polymer with an N,N-dimethylacetamide (DMAc) solution. The manufacturing process of the solid capacitor includes the following steps. 【0038】 Step (1) was the same as step (1) of Example 1. 【0039】 (2) The second wound body was placed in a sealed container containing an n-type conductive polymer solution and vacuum impregnated at a vacuum of 0.1 MPa, an impregnation temperature of 50°C, and an impregnation time of 20 minutes. After that, it was vacuum dried at 80°C for 150 minutes, and the above "vacuum impregnation and vacuum drying" step was repeated twice to obtain the third wound body. 【0040】 The n-type conductive polymer solution was prepared by the following method: 1 mmol of 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione, 1 mmol of 3,7-dihydrobenzo[1,2-b:4,5-b']dithiophene-2,6-dione, and 0.1 mmol of copper acetate (an oxidizing agent) were dissolved in 10 mL of DMAc and reacted at 65°C with stirring in an air atmosphere for 30 minutes. The system was then diluted with DMAc to a solid content of approximately 20 mg / mL and filtered through a 22 μm mesh polytetrafluoroethylene filter to obtain the n-type conductive polymer solution (where the concentration of n-type conductive polymer II is 2 wt%, and the remainder is DMAc). The related reactions are as follows. 【0041】 [ka] 【0042】 The n-type conductive polymer II obtained by the above reaction has a number-average molecular weight of M n The conductivity was 2468 kDa, the average conductivity was 1260 S / cm, n1:n21, m≒0.6(n1+n2), y≒0.05m, and z≒0.01m. 【0043】 (3) The third coil was fixed inside the lead case, assembled, and sealed to obtain a semi-finished capacitor. By charging and aging semi-finished capacitors, we obtained finished solid capacitors. The performance of the solid capacitor obtained in this embodiment was tested, and the detailed test results are shown in Table 1. 【0044】 Example 3 Electrolytic capacitor based on n-type conductive polymer: In this embodiment, a 16V 47μF 6.3×11 solid capacitor was obtained by polymerizing an n-type conductive polymer monomer in position through stepwise impregnation. The manufacturing process of the solid capacitor includes the following steps. 【0045】 Step (1) was the same as step (1) of Example 1. 【0046】 (2) 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione (1 mmol) was dissolved in 5 mL of DMSO to obtain an n-type conductive polymer monomer solution, and manganese acetate (1 mmol) was used as an oxidizing agent and dissolved in 5 mL of DMSO to obtain an oxidizing agent solution. 【0047】 The second wound material was placed in the above-mentioned n-type conductive polymer monomer solution and impregnated at room temperature and atmospheric pressure for 10 minutes. After that, it was removed and vacuum-dried at 80°C for 30 mm. Then, it was placed in the above-mentioned oxidizing agent solution and impregnated at room temperature and atmospheric pressure for 2 mm. After that, it was removed and vacuum-dried at 80°C for 5 minutes. The steps of impregnation with the n-type conductive polymer monomer solution, vacuum drying, impregnation with the oxidizing agent solution, and vacuum drying were repeated in this order three times to obtain the third wound material. The monomers were polymerized in situ in the order of the above steps to obtain the corresponding n-type conductive polymer (although the molecular weight cannot be tested because the above situ polymerization is a precipitation reaction, polymer powder was obtained under the same conditions, and the average conductivity of the n-type conductive polymer obtained in this example was tested by pressing the powder, and the result was 680 S / cm). 【0048】 (3) The third coil was fixed inside the aluminum case, assembled, and sealed to obtain a semi-finished capacitor. By charging and aging semi-finished capacitors, we obtained finished solid capacitors. The performance of the solid capacitor obtained in this embodiment was tested, and the detailed test results are shown in Table 1. 【0049】 Example 4 Electrolytic capacitor based on n-type conductive polymer: In this embodiment, a 16V 470μF 6.3×11 solid capacitor was manufactured by polymerizing an n-type conductive polymer monomer in situ using a drop-drop method. The manufacturing process of the solid capacitor includes the following steps. 【0050】 Step (1) was the same as step (1) of Example 1. 【0051】 (2) 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione (1 mmol) and duloquinone oxidizing agent (1.5 mmol) were dissolved together in 5 mL of DMSO and stirred at 60°C for 30 minutes to obtain a monomer-oxidizing agent mixed solution. 【0052】 A monomer-oxidant mixture was injected into the second wound body using a quantitative syringe, and the mixture was heated and polymerized in a nitrogen atmosphere at 80°C for 3 hours, followed by vacuum drying at 80°C for 30 minutes. The heating polymerization and vacuum drying steps were repeated in this order twice to obtain the third wound body. The monomers were polymerized in situ in the order of the above steps to obtain the corresponding n-type conductive polymer (although the molecular weight of the polymer cannot be tested by the above situ polymerization, polymer powder was obtained under the same conditions, and the average conductivity of the n-type conductive polymer obtained in this example was tested by pressing the powder, resulting in a value of 4200 S / cm). 【0053】 (3) The third winding was fixed inside the lead case, assembled, and sealed to obtain a semi-finished capacitor. The semi-finished capacitor was charged and aged to obtain a finished solid capacitor. The performance of the solid capacitor obtained in this embodiment was tested, and the detailed test results are shown in Table 1. 【0054】 Example 5 Electrolytic capacitor based on n-type conductive polymer: In this embodiment, a 16V 470μF 6.3×11 solid capacitor was manufactured by polymerizing an n-type conductive polymer monomer in situ using a drop-drop method, and forming counterions of the conductive polymer with additives during polymerization. The manufacturing process of the solid capacitor includes the following steps. 【0055】 Step (1) was the same as step (1) of Example 1. 【0056】 (2) 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione (1 mmol), duloquinone (1.5 mmol) as an oxidizing agent, and 1-ethylpyridinium bromide (1 mmol) as an additive were dissolved together in 5 mL of DMSO and stirred at 60°C for 30 minutes to obtain a monomer-oxidizing agent-additive mixed solution. 【0057】 The mixed solution was injected into the second wound body using a quantitative syringe, and then heated and polymerized in a nitrogen atmosphere at 80°C for 3 hours. After that, it was vacuum dried at 80°C for 30 minutes. The steps of heating polymerization and vacuum drying were repeated in this order twice. The relevant chemical reaction equation is as follows. 【0058】 [ka] 【0059】 Although the molecular weight of the polymer obtained by the above in-situ polymerization cannot be tested, polymer powder was obtained under the same conditions, and the powder was pressed to test the average conductivity of the n-type conductive polymer obtained in this example. The result was 1800 S / cm, where m ≈ 0.8n and y ≈ 0.7m. 【0060】 (3) The third winding was fixed inside the lead case, assembled, and sealed to obtain a semi-finished capacitor. The semi-finished capacitor was charged and aged to obtain a finished solid capacitor. The performance of the solid capacitor obtained in this embodiment was tested, and the detailed test results are shown in Table 1. 【0061】 Comparative Example 1 This comparative example provides a method for manufacturing a 16V 470μF 6.3×11 solid capacitor using a p-type conductive polymer PEDOT:PSS dispersion, and the manufacturing method is as follows. 【0062】 Step (1) was the same as step (1) of Example 1. 【0063】 (2) A commercially available PEDOT:PSS aqueous solution was used, where the mass fraction of PEDOT:PSS was in the range of 1% to 3%, and the particle size of the solid material in the dispersion was 100 nm or less. The second coiled body was placed in the PEDOT:PSS aqueous solution and pressurized and impregnated using a hydraulic impregnation device, with the impregnation conditions being the same as in step (2) of Example 1. The above steps of "pressure impregnation and vacuum drying" were repeated twice to obtain the third coiled body. 【0064】 Step (3) was the same as step (3) in Example 1. The performance of the solid capacitor obtained in this comparative example was tested, and the detailed test results are shown in Table 1. 【0065】 Example 6 Electrolytic capacitor based on n-type conductive polymer: In this embodiment, a 16V 470μF 6.3×11 solid-liquid mixed capacitor was manufactured by impregnating an n-type conductive polymer with a DMSO solution. The manufacturing process of the solid-liquid mixed capacitor includes the following steps. 【0066】 Steps (1) and (2) were the same as steps (1) and (2) of Example 1. 【0067】 (3) The third coil was placed in a sealed container containing the electrolyte and vacuum-impregnated for 10 minutes under a relative negative pressure of -90 kPa. The electrolyte consisted of 15 wt% ethylene glycol, 50 wt% γ-butyrolactone, 15 wt% sulfolane, and 20 wt% tetrabutylammonium hexafluorophosphate. The third winding, impregnated with electrolyte, was fixed to a lead case, assembled, and sealed to obtain a semi-finished capacitor. The semi-finished capacitor was charged and aged to obtain a finished solid-liquid mixed capacitor. The performance of the solid-liquid mixed condenser obtained in this embodiment was tested, and the detailed test results are shown in Table 1. 【0068】 Example 7 Electrolytic capacitor based on n-type conductive polymer: In this embodiment, a 2.5V 1.1mF 6.3×8 solid capacitor was manufactured by impregnating an n-type conductive polymer with a DMSO solution. The manufacturing process of the solid capacitor includes the following steps. 【0069】 Step (1) was the same as step (1) of Example 1. 【0070】 (2) The n-type conductive polymer solution prepared in step (2) of Example 1 (where the concentration of n-type conductive polymer I is 1 wt%, and the remainder is DMSO) was diluted with DMSO to a solid content of 5 wt%, and the diluted solution was homogenized on a homogenizing table and uniformly mixed to obtain an n-type conductive polymer solution with a solid content of 0.5 wt%. 【0071】 The second wound body was placed in a sealed container containing an n-type conductive polymer solution (solid content 5 wt%), and vacuum impregnated at a vacuum of 0.1 MPa, an impregnation temperature of 50°C, and an impregnation time of 5 minutes. Subsequently, it was vacuum dried at 80°C for 150 minutes. The above "vacuum impregnation and vacuum drying" step was repeated twice to obtain the third wound body. 【0072】 (3) The third winding was fixed inside the lead case, assembled, and sealed to obtain a semi-finished capacitor. The semi-finished capacitor was charged and aged to obtain a finished solid capacitor. 【0073】 Test example Relevant electrical performance tests were performed on the capacitors manufactured based on the n-type conductive polymer in the examples and the solid capacitors manufactured based on the p-type conductive polymer PEDOT:PSS in the comparative examples. Capacitance (CAP), dielectric loss tangent (DF), equivalent series resistance (ESR), and leakage current (LC) were tested in accordance with GB / T6346.25-2018 "Fixed Capacitors for Electronic Equipment - Part 25: Section Specification - Surface Mount Conductive Polymer Solid Electrolytes - Lead Fixed Capacitors". The test conditions for capacitance and dielectric loss tangent were 20°C and 120Hz, the test conditions for equivalent series resistance were 20°C and 100Hz, and the test conditions for leakage current were 20°C and 2 minutes. The initial performance of the capacitors is shown in Table 1. The capacitors of the examples and comparative examples were continuously operated for 1000 to 4000 hours at 85°C and 85% humidity (double 85 conditions) to test their electrical characteristics. The test results are shown in Table 2. 【0074】 [Table 1] 【0075】 [Table 2] 【0076】 As can be seen from Tables 1 and 2, comparing Example 1 and Comparative Example 1, the solid or solid-liquid mixed capacitors manufactured using the n-type conductive polymer of the present invention have a relatively higher capacitance extraction rate and a significantly lower high-frequency ESR value than the capacitors manufactured using the p-type conductive polymer PEDOT. This is because the manufacturing method based on the n-type conductive polymer of the present invention allows for complete impregnation of the capacitor, and the conductivity of the n-type conductive polymer is higher than that of the p-type. More importantly, in the present invention, the solid or solid-liquid mixed capacitors manufactured using the n-type conductive polymer have more stable device performance under double 85 conditions, which helps extend the service life of the capacitor under extreme conditions. 【0077】 The above describes only preferred specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should know that equivalent substitutions or modifications based on the technical solutions and inventive concepts of the present invention, within the scope of the technical scope disclosed herein, should be included within the scope of protection of the present invention.

Claims

[Claim 1] An electrolytic capacitor based on an n-type conductive polymer, comprising a wound body formed by laminating and winding a negative electrode foil, electrolytic paper, and a positive electrode foil with an oxide film dielectric formed on its surface in this order, The aforementioned wound body has an n-type conductive polymer electrolyte layer inside, The material of the n-type conductive polymer electrolyte layer contains one or more types of n-type conductive polymers, and the n-type conductive polymers contain repeating units of the following negatively charged conjugated structure. An electrolytic capacitor characterized by the following features. 【Chemistry 1】 (Here, X is one of oxygen, sulfur, selenium, tellurium, or nitrogen atoms, and if X is a nitrogen atom, R is one of hydrogen, linear alkyl, or isoalkyl, and if X is one of oxygen, sulfur, selenium, or tellurium atoms, R does not exist, Y ＋ (wherein represents a cation, the repeating units of the negatively charged conjugated structure are either identical or different.) [Claim 2] The conductivity of the n-type conductive polymer is 500 S / cm to 8000 S / cm, and the molecular weight of the n-type conductive polymer is at least 1 kDa. The electrolytic capacitor based on an n-type conductive polymer according to claim 1, characterized in that the cation is one or more selected from hydrogen ions, ammonium ions, pyridinium salt ions, and metal ions. [Claim 3] The electrolytic capacitor is characterized by comprising an electrolyte in which the wound body is immersed, a case for housing the wound body and the electrolyte, and a sealing member for sealing the case, wherein the electrolytic capacitor is based on an n-type conductive polymer according to claim 1 or 2. [Claim 4] The aforementioned case is a case made of metal, The electrolytic paper is selected from synthetic fibers and / or natural fibers. The positive electrode foil and the negative electrode foil are each made of aluminum valve metal, and the positive electrode foil and the negative electrode foil each have pull-out pins. An electrolytic capacitor based on the n-type conductive polymer according to claim 3, characterized in that... [Claim 5] A manufacturing process for an electrolytic capacitor based on an n-type conductive polymer according to any one of claims 1 to 4, Step (1) involves winding a positive electrode foil, electrolytic paper, and negative electrode foil in this order to form a first winding body of a desired standard, and subjecting the first winding body to at least one formation process, which includes forming and drying, to obtain a second winding body. Step (2) is to form the electrolyte layer having the n-type conductive polymer inside the second wound body to obtain a third wound body, Step (3) involves placing the capacitor in a case, sealing it, and then applying electricity to age it, thereby obtaining an electrolytic capacitor based on an n-type conductive polymer. A manufacturing process characterized by including the following. [Claim 6] The process for manufacturing an electrolytic capacitor based on an n-type conductive polymer according to claim 5, wherein in step (2), the step of forming an electrolyte layer having the n-type conductive polymer is to impregnate the second wound body in an n-type conductive polymer solution at least once, the impregnation treatment comprising impregnation followed by drying, and the n-type conductive polymer solution contains one or more types of the n-type conductive polymer. [Claim 7] The n-type conductive polymer solution contains 0.1 wt% to 10 wt% of the n-type conductive polymer and an organic solvent. A process for manufacturing an electrolytic capacitor based on an n-type conductive polymer according to claim 6, characterized in that the organic solvent is one or more selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, amines, esters, ethers, ketones, dimethyl sulfoxides, amides, and sulfolanes. [Claim 8] In step (2), the step of forming the electrolyte layer having the n-type conductive polymer involves performing the steps of impregnation with an n-type conductive polymer monomer solution, drying, impregnation with an oxidizing agent solution, and drying on the second wound body at least once in this order by a stepwise impregnation method to obtain the third wound body, wherein the n-type conductive polymer monomer solution contains one or more types of n-type conductive polymer monomers. Alternatively, in step (2), the step of forming the electrolyte layer having the n-type conductive polymer involves dropping a mixed solution containing both one or more n-type conductive polymer monomers and an oxidizing agent onto the second wound body at least once by a dropwise method, then performing thermal polymerization at least once, and then drying to obtain the third wound body. A manufacturing process for an electrolytic capacitor based on an n-type conductive polymer according to claim 5, characterized in that the n-type conductive polymer monomer has the following structure. 【Chemistry 2】 (Here, X is one of the following atoms: oxygen, sulfur, selenium, tellurium, or nitrogen. If X is a nitrogen atom, R is one of the following atoms: hydrogen, linear alkyl, or isoalkyl. If X is one of the following atoms: oxygen, sulfur, selenium, or tellurium, R does not exist.) [Claim 9] In step (2) employing a stepwise impregnation method, the n-type conductive polymer monomer solution contains 0.1 wt% to 5 wt% of the n-type conductive polymer monomer and an organic solvent, and the oxidizing agent solution contains 0.1 wt% to 10 wt% of the oxidizing agent and an organic solvent. In step (2) employing a dropwise addition method, the thermal polymerization is carried out under nitrogen protection at 50°C to 150°C, wherein the mixed solution containing both one or more types of n-type conductive polymer monomers and an oxidizing agent contains the n-type conductive polymer monomers, the oxidizing agent, and an organic solvent, the mass concentration of the n-type conductive polymer monomer being 1 wt% to 5 wt%, and the mass concentration of the oxidizing agent being 1 wt% to 5 wt%. A process for manufacturing an electrolytic capacitor based on an n-type conductive polymer according to claim 8, characterized in that the oxidizing agent is one or more selected from oxygen gas, peroxides, metal salts, persulfates, perborates, hypohalites, quinone compounds, and perbenzoic acids, and the organic solvent is one or more selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, amines, esters, ethers, ketones, dimethyl sulfoxides, amides, and sulfolanes. [Claim 10] Step (2), which employs a stepwise impregnation method, further includes the step of impregnation with an additive compound solution after the steps of impregnation with the oxidizing agent solution and drying, wherein the additive compound solution contains an additive compound. In step (2) employing a dropwise method, the mixed solution further contains an additive compound. A manufacturing process for an electrolytic capacitor based on an n-type conductive polymer according to claim 9, characterized in that the additive compound comprises one or more of pyridine compounds and quaternary ammonium compounds. [Claim 11] In step (2), pressure impregnation or vacuum negative pressure impregnation is employed as the impregnation method. The manufacturing process for an electrolytic capacitor based on an n-type conductive polymer according to claim 6 or 8, characterized in that in step (2), the drying is performed at a temperature of 80°C to 150°C and for a time of 5 minutes to 300 minutes. [Claim 12] In step (1), the drying is performed at a temperature of 80°C to 150°C for a duration of 5 minutes to 300 minutes. A manufacturing process for an electrolytic capacitor based on an n-type conductive polymer according to claim 5, characterized in that, before forming the first winding, lead pins are crimped to the positive and negative foils, respectively, and in step (1), the formation is characterized by immersing the first winding in a formation liquid and then applying a formation voltage the same as the voltage of the anode foil of the first winding. [Claim 13] Step (3) further comprises impregnating the third wound body with an electrolyte and impregnating the third wound body in the electrolyte for 5 to 10 minutes using a relative negative pressure of -90 kPa, the manufacturing process of an electrolytic capacitor based on an n-type conductive polymer according to claim 5.

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