WO2016123826A1 - 一种固体电解质铝电解电容器及其制造方法 - Google Patents

一种固体电解质铝电解电容器及其制造方法 Download PDF

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Publication number
WO2016123826A1
WO2016123826A1 PCT/CN2015/073533 CN2015073533W WO2016123826A1 WO 2016123826 A1 WO2016123826 A1 WO 2016123826A1 CN 2015073533 W CN2015073533 W CN 2015073533W WO 2016123826 A1 WO2016123826 A1 WO 2016123826A1
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Prior art keywords
core package
dispersion
solid electrolyte
electrolytic capacitor
core
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PCT/CN2015/073533
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English (en)
French (fr)
Inventor
刘泳澎
马彦斌
袁永
罗伟
郑萍
廖琼
李慧峰
吴棣荣
伍伟桥
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肇庆绿宝石电子科技股份有限公司
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Publication of WO2016123826A1 publication Critical patent/WO2016123826A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors

Definitions

  • the invention relates to the technical field of preparation of electrolytic capacitors, and in particular to a solid electrolyte aluminum electrolytic capacitor and a manufacturing method thereof.
  • solid electrolytic capacitors Compared with ordinary liquid electrolytic capacitors, solid electrolytic capacitors have outstanding electrical properties, low equivalent series resistance (ESR), high ripple current resistance, long service life and stable performance. With the continuous upgrading of electronic products, the functions and performances of the electronic products continue to improve, and the high-frequency characteristics of capacitors are becoming higher and higher. People reduce the ESR of solid electrolytic capacitors in various ways to meet the high-frequency characteristics of capacitors. .
  • the oxidant itself has a strong acidity, which has a great destructive effect on the oxide film of the positive electrode foil, greatly reducing the original voltage value of the positive electrode foil, and the other is because the monomer and The oxidant is dissolved in the solvent and impregnated into the core package. Because the solvent and the positive foil of the electrode have good wettability, the oxidant and the monomer are brought into the corroded micropores of the anode foil because the micropores are formed into oxide films when formed. The weak place, combined with the solid electrolyte has no repair ability, the pressure resistance of this place is low, when a certain voltage is applied, a large leakage current will be generated to make the product fail.
  • the technical solution is to polymerize the conductive polymer in water to form a dispersion of water, and then immerse it into the core package by impregnation.
  • the capacitor thus formed has no oxidant damage to the foil, so that the product is
  • the pressure resistance is increased, and the polymer dispersed in water has a certain size. Due to dispersion in water, the water is less wet than the general solvent, which ensures that the micropores of the positive electrode are immersed in the conductive polymer. This place where the withstand voltage is weak is not able to form a large leakage due to the lack of polymer, so the pressure resistance of the product can be greatly improved.
  • the present invention provides a solid electrolyte aluminum electrolytic capacitor having excellent ESR performance, wherein the solid electrolyte is a conductive polymer and a conductive carbon material, and the conductive polymer resistance at a high temperature can be solved remarkably. Increase problems and low performance.
  • the invention also provides a manufacturing method of the solid electrolyte aluminum electrolytic capacitor, which mainly solves the problem that the micropores cannot be immersed or immersed in a very small amount of the conductive polymer and the conductive carbon material by impregnating the core package under different pressure environments.
  • the problem is not only to improve the withstand voltage, but also to optimize the impregnation process to ensure that there are more solid electrolytes in the impregnable area and the distribution is uniform.
  • the manufacturing method can obtain a solid capacitor with a lower ESR value and a higher withstand voltage value, and at the same time obtain a lower leakage current, the same Good batch consistency was also obtained.
  • the invention provides a solid electrolyte aluminum electrolytic capacitor comprising an aluminum shell and a core package disposed in the aluminum shell, the core package comprising an anodized aluminum foil, a cathode foil, and the anodized aluminum foil and the cathode foil
  • the conductive polymer is poly 3,4 ethylene dioxythiophene.
  • the conductive carbon material is a carbon nano material or a carbon nano composite material.
  • the invention also provides a method for manufacturing the solid electrolyte aluminum electrolytic capacitor, comprising:
  • the core of the capacitor is soldered to the iron bar, and a voltage is applied to form, and after being formed, it is washed and dried;
  • the core package is placed at 65 ⁇ 100 ° C for 20 ⁇ 60min, and then the core package is placed at 135 ⁇ 165 ° C for 20 ⁇ 60min;
  • Steps (3) to (6) are repeated at least once;
  • the dispersion B is a dispersion containing a conductive polymer and a conductive carbon material.
  • the invention provides a method for manufacturing a solid electrolyte aluminum electrolytic capacitor, comprising:
  • the core of the capacitor is soldered to the iron bar, and a voltage is applied to form, and after being formed, it is washed and dried;
  • the impregnation time is 1 to 30 min
  • the core package is placed at 65 ⁇ 100 ° C for 20 ⁇ 60min, and then the core package is placed at 135 ⁇ 165 ° C for 20 ⁇ 60min;
  • the impregnation time is 1 to 30 min
  • the core package is dried at 65 ⁇ 100 ° C for 20 ⁇ 60min, and then the core package is placed at 135 ⁇ 165 ° C for 20 ⁇ 60min;
  • Steps (3) to (8) are repeated at least once;
  • the dispersion A and the dispersion C are a dispersion containing a conductive polymer and a dispersion containing a conductive carbon material, respectively.
  • the invention further provides a method for manufacturing a solid electrolyte aluminum electrolytic capacitor, comprising:
  • the core of the capacitor is soldered to the iron bar, and a voltage is applied to form, and after being formed, it is washed and dried;
  • the impregnation time is 1 to 30 min
  • the core package is dried at 65 ⁇ 100 ° C for 20 ⁇ 60min, and then the core package is placed at 135 ⁇ 165 ° C for 20 ⁇ 60min;
  • the impregnation time is 1 to 30 min
  • the core package is removed from the dispersion A, and the core package is immersed in the dispersion A after vacuuming, and the impregnation time is 1 to 10 min;
  • the core package is dried at 65 ⁇ 100 ° C for 20 ⁇ 60min, and then the core package is placed at 135 ⁇ 165 ° C for 20 ⁇ 60min;
  • Steps (5) to (8) are repeated at least once;
  • the dispersion A and the dispersion C are a dispersion containing a conductive polymer and a dispersion containing a conductive carbon material, respectively.
  • the degree of vacuum of the vacuum in the step (3) is 700 to 970 Pa.
  • the pressurized air is introduced into the compressed air and pressurized to 0.1 to 0.6 MPa.
  • the step (9) is repeated 5 times for the steps (3) to (8).
  • the conductive carbon material is a carbon nano material or a carbon nano composite material; the carbon nano material is carbon nanotube or graphene.
  • the present invention has the following beneficial effects:
  • the electrolyte in the dispersion can more stably form a stable conductive polymer layer and conduct electricity on the surface of the foil.
  • the carbon layer improves the electrical performance of the capacitor; at the same time, the conductive polymer and the conductive carbon material act as a solid electrolyte, which can effectively improve the withstand voltage value of the solid electrolyte aluminum electrolytic capacitor;
  • the invention adopts multiple repeated impregnation steps, and removes the core package of the impregnation solvent after heat treatment, which is beneficial to the absorption of the impregnation liquid next time, and can obtain a lower ESR solid electrolyte aluminum electrolytic capacitor, thereby improving the extraction rate and reducing the loss.
  • the product consistency can be improved, especially for large-sized capacitors, for example, larger than 10*12mm size; the manufacturing method further improves production efficiency, facilitates scale-up, and automated production;
  • the capacitor is a solid electrolyte composed of a conductive carbon material composite conductive polymer, which reduces the solid electrolyte resistance, so that the capacitor has a low equivalent series resistance.
  • the present invention solves the technical problem that the aluminum cathode has a large electrical resistance when it is in contact with the solid electrolyte, and the solid electrolytic capacitor provided by the invention has the advantages of high stability and reliability, low equivalent series resistance and small leakage current. It can work in high and low temperature environments for a long time and maintains stable performance.
  • the present invention provides a solid electrolyte aluminum electrolytic capacitor comprising an aluminum shell and a core package disposed in the aluminum shell, the core package being connected to the positive and negative terminals, and the outer surface of the positive and negative terminals is plated with a silver plating layer
  • the core package is provided with a rubber cover or a rubber stopper.
  • the core package includes an anodized aluminum foil, a cathode foil, an electrolytic paper interposed between the anodized aluminum foil and a cathode foil, and a solid electrolyte,
  • the solid electrolyte may be a conductive polymer or a composite of a conductive polymer and a conductive carbon material.
  • the solid electrolyte is obtained by polymerization of a dispersion of a conductive polymer and/or a conductive carbon material.
  • the anodized aluminum foil is a JCC anode foil manufactured by Nippon Electric Storage Co., Ltd., and has a model of HGF110J16-365VF-1.33 ⁇ F, a width of 17 mm, and a length of 491 mm; and the cathode foil is a Nanofoil cathode foil.
  • Its model is NF3000, the width is 17mm, the length is 521mm; the electrolytic paper is Asahi Kasel DS040060, and its width is 20mm.
  • the solid electrolyte may be a conductive polymer; or may be a physical mixture or composition of a conductive polymer and a conductive carbon material, which may be mixed with each other to form a solid electrolyte through a conductive polymer and a conductive carbon material, and may also pass
  • the conductive polymer and the conductive carbon material are laminated to each other to form a solid electrolyte, but are not limited thereto.
  • the dispersion A and the dispersion C used in the present invention are a dispersion containing a conductive polymer and a dispersion containing a conductive carbon material, respectively; and the dispersion B is a dispersion containing a conductive polymer and a conductive carbon material.
  • the conductive polymer is polyaniline and/or polypyrrole and/or polythiophene and/or poly 3,4 ethylene dioxythiophene.
  • the concentration of the conductive polymer is preferably, but not limited to, 2 to 3% by weight.
  • the conductive carbon material is a carbon nano material or a carbon nano composite material, and the conductive carbon material preferably has a graphene particle diameter of less than 200 nm and a carbon nanotube length of 2 to 200 nm.
  • the carbon nanomaterial is carbon nanotube or graphene;
  • the active material in the carbon nanocomposite is one or more of the following materials: a conductive polymer, a metal oxide, a mixture between conductive polymers, a mixture between a conductive polymer and a metal oxide, a mixture between metal oxides, a composite between conductive polymers, a composite between a conductive polymer and a metal oxide, a complex between metal oxides .
  • the ethanol solution is placed in a high-speed shearing machine at a shear rate of 20,000 rpm, and the hexene or carbon nanotube or carbon nanocomposite is slowly added to the stirred alcohol solution.
  • the stirring time is controlled to be more than 30 min, and is prepared as a dispersion containing a conductive carbon material, that is, dispersion C.
  • the concentration of the conductive carbon material-containing alcohol dispersion is controlled to be between 0.5 and 5% by weight, and a dispersing agent such as sodium dodecyl sulfate (SDS) or sodium dodecylbenzenesulfonate may be added in an appropriate amount. (SDBS).
  • SDS sodium dodecyl sulfate
  • SDBS sodium dodecylbenzenesulfonate
  • the ethanol solution is placed in a high-speed shearing machine at a shear rate of 20,000 rpm, and the hexene or carbon nanotube or carbon nanocomposite is slowly added to the stirred alcohol solution.
  • the concentration of the conductive carbon material is controlled between 0.5 and 5% by weight, and then the conductive polymer is added.
  • the concentration of the conductive polymer can be controlled between 2 and 3% by weight, and the stirring time is controlled to be more than 30 minutes.
  • a dispersion containing a conductive carbon material and a conductive polymer, that is, dispersion B, may be added with a dispersing agent such as sodium dodecyl sulfate (SDS) or sodium dodecylbenzenesulfonate (SDBS) in an appropriate amount.
  • a dispersing agent such as sodium dodecyl sulfate (SDS) or sodium dodecylbenzenesulfonate (SDBS) in an appropriate amount.
  • the present invention provides a method of manufacturing a solid electrolyte aluminum electrolytic capacitor, the solid electrolyte being a conductive polymer; the manufacturing method specifically includes:
  • Anodized aluminum foil and cathode foil are wound together into a core package by electrolytic paper, and the anode of the core package is welded to the iron bar, and the core package is immersed in the chemical conversion liquid, and a constant voltage is applied according to the voltage of the positive foil to form a core.
  • the time is not less than 20 minutes, and the chemical conversion liquid may be a phosphoric acid-based chemical conversion liquid, a boric acid-based chemical conversion liquid or an ammonium adipic acid-based chemical conversion liquid;
  • the core package is immersed in pure water of 40 to 100 ° C for 30 to 60 minutes to remove the residual components in the chemical conversion liquid, and then dried. Drying is divided into two steps. The first step is to dry at a low temperature. The temperature of drying is controlled at 50-100 °C. The temperature is too low, which will affect the drying effect. When it exceeds 100 °C, the liquid will boil in the product, which will affect the product. characteristic. The drying time is 20 to 100 minutes, ensuring that there is no sufficient amount of water to boil in the core package.
  • the second step of drying is 110 ⁇ 200 ° C, to ensure that the residual moisture is fully volatilized, the temperature should not be too high, too high will hurt the lead pin phenomenon, the drying time is 20 ⁇ 60min, the time is too short, there will be no water Volatilization will affect the next impregnation effect and the characteristics of the product. If the time is too long, the anode foil of the product will deteriorate and affect the performance of the product.
  • the impregnation time is 1 to 30 min
  • the impregnation time is 1 to 10 min
  • Steps (3) to (6) are repeated at least once, preferably but not limited to five times.
  • the dispersion A has a low solid content of the polymer, and less impregnation introduces less polymer at a time, which will affect the consistency of the product, the ESR will be slightly higher, the loss will be large, and too little, and the life of the product cannot be guaranteed. Repeat the impregnation several times according to actual needs.
  • the aluminum shell was placed, sealed with a rubber stopper, and aged to obtain a solid electrolyte aluminum electrolytic capacitor.
  • the method of aging is to put the product into an environment of 85-150 ° C, apply 0.2 times of rated voltage, 20-100 min, then apply 0.5 times of rated voltage for 20-100 min, then apply 0.8 times of rated voltage for 20-100 min, and then apply 1.0 times.
  • the rated voltage is 20 ⁇ 100min, and then the rated voltage of 1.2 times can be applied for 20 ⁇ 100min.
  • the present invention also provides a method of manufacturing a solid electrolyte aluminum electrolytic capacitor which is a conductive polymer and a conductive carbon material.
  • the manufacturing method specifically includes:
  • Anodized aluminum foil and cathode foil are wound together into a core package by electrolytic paper, and the anode of the core package is welded to the iron bar, and the core package is immersed in the chemical conversion liquid, and a constant voltage is applied according to the voltage of the positive foil to form a core.
  • the time is not less than 20 min; after the formation, the core package is immersed in 40-100 ° C pure water for 30-60 min to remove the residual components in the chemical conversion solution, and then dried at 50-100 ° C for 20-100 min, then dried at 110-200 ° C. 20 to 60 minutes;
  • the impregnation time is 1 to 10 min
  • Steps (3) to (6) are repeated at least once, preferably but not limited to five times.
  • the aluminum shell was placed, sealed with a rubber stopper, and aged to obtain a solid electrolyte aluminum electrolytic capacitor.
  • the present invention also provides a method of manufacturing a solid electrolyte aluminum electrolytic capacitor which is a conductive polymer and a conductive carbon material.
  • the manufacturing method specifically includes:
  • Anodized aluminum foil and cathode foil are wound together into a core package by electrolytic paper, and the anode of the core package is welded to the iron bar, and the core package is immersed in the chemical conversion liquid, and a constant voltage is applied according to the voltage of the positive foil to form a core.
  • the time is not less than 20 min; after the formation, the core package is immersed in 40-100 ° C pure water for 30-60 min to remove the residual components in the chemical conversion solution, and then dried at 50-100 ° C for 20-100 min, then dried at 110-200 ° C. 20 to 60 minutes;
  • the impregnation time is 1 to 30 min
  • the core package is placed at 65 ⁇ 100 ° C for 20 ⁇ 60min, and then the core package is placed at 135 ⁇ 165 ° C for 20 ⁇ 60min;
  • the impregnation time is 1 to 30 min
  • the core package is dried at 65 ⁇ 100 ° C for 20 ⁇ 60min, and then the core package is placed at 135 ⁇ 165 ° C for 20 ⁇ 60min;
  • Steps (3) to (8) are repeated at least once;
  • the present invention further provides a method of manufacturing a solid electrolyte aluminum electrolytic capacitor which is a conductive polymer and a conductive carbon material.
  • the manufacturing method specifically includes:
  • Anodized aluminum foil and cathode foil are wound together into a core package by electrolytic paper, and the anode of the core package is welded to the iron bar, and the core package is immersed in the chemical conversion liquid, and a constant voltage is applied according to the voltage of the positive foil to form a core.
  • the time is not less than 20 min; after the formation, the core package is immersed in 40-100 ° C pure water for 30-60 min to remove the residual components in the chemical conversion solution, and then dried at 50-100 ° C for 20-100 min, then dried at 110-200 ° C. 20 to 60 minutes;
  • the core package is placed at 65 ⁇ 100 ° C for 20 ⁇ 60min, and then the core package is placed at 135 ⁇ 165 ° C for 20 ⁇ 60min;
  • the impregnation time is 1 to 30 min
  • the core package is dried at 65 ⁇ 100 ° C for 20 ⁇ 60min, and then the core package is placed at 135 ⁇ 165 ° C for 20 ⁇ 60min;
  • Steps (3) to (8) are repeated at least once;
  • the vacuum state and the pressurized state according to the present invention may be implemented on one device or both, but it is preferably implemented on one device while the core package and the dispersion are simultaneously in a vacuum or a normal pressure or a pressurized state.
  • the manufacturing method is applicable not only to a high-pressure solid electrolyte aluminum electrolytic capacitor but also to a solid electrolytic capacitor such as tantalum, niobium or titanium.
  • the conductive polymer used in the dispersion A of the present embodiment is poly 3,4 ethylenedioxythiophene having a particle diameter of about 40 to 80 nm, preferably 60 nm.
  • the capacitor size is 200V100 ⁇ F and the size is ⁇ 16*26mm.
  • the capacitor is manufactured by:
  • JCC anode foil manufactured by Nippon Electric Storage Industry Co., Ltd.
  • model number HGF110J16-365VF-1.33 ⁇ F width 17mm, length 491mm
  • Nanofoil cathode foil model NF3000, width 17mm, length 521mm
  • Electrolytic paper Asahi Kasel ADS040060 width 20mm.
  • the anode foil and the cathode foil are wound together into a core package by electrolytic paper, the anode of the core package is welded to the iron bar, the core package is immersed in the chemical conversion liquid, and a voltage of 365 V is applied according to the voltage of the positive foil in the phosphoric acid chemical conversion liquid. After formation, the core package is immersed in 70 ° C pure water for 30 minutes to remove the residual components in the chemical solution, and then dried at 75 ° C for 60 min and then dried at 150 ° C for 30 min;
  • Steps (3) to (4) are cycled 5 times;
  • the aluminum shell is filled, sealed with a rubber stopper, and aged to obtain a solid electrolyte aluminum electrolytic capacitor.
  • the method of aging is to put the product into the environment of 110 ° C, apply 0.2 times of rated voltage, 80 min, then apply 0.5 times of rated voltage for 60 min, then apply 0.8 times of rated voltage for 40 min, then apply 1.0 times of rated voltage for 20 min, then apply 1.2 times.
  • the rated voltage can be 20min.
  • Table 1 shows the performance test of the capacitor prepared in Example 1.
  • step (3) the core package was retained in the dispersion A, and compressed air was introduced for pressurization. Up to 0.5 MPa, the impregnation time is 5 min, the other steps and their order are unchanged; the analysis results are shown in Table 2.
  • Table 2 shows the performance test of the capacitor prepared in Example 2.
  • the capacitor size was 200V100 ⁇ F, and the size was ⁇ 16*26mm, which was different.
  • Table 3 shows the performance test of the capacitor prepared in Example 3.
  • Table 4 shows the performance test of the capacitor prepared in Example 4.
  • the capacitor is manufactured by:
  • JCC anode foil model number is HGF110J16-365VF-1.33 ⁇ F, width 17mm, length 491mm; Nanofoil cathode foil, model NF3000, width 17mm, length 521mm; electrolytic paper Asahi Kasel ADS040060, width is 20mm, the capacitor is made of 200V100 ⁇ F and the size is ⁇ 16*26mm.
  • the anode foil and the cathode foil are wound together into a core package by electrolytic paper, the anode of the core package is welded to the iron bar, the core package is immersed in the chemical conversion liquid, and a voltage of 365 V is applied according to the voltage of the positive foil in the phosphoric acid chemical conversion liquid. After formation, the core package is immersed in 70 ° C pure water for 30 minutes to remove the residual components in the chemical solution, and then dried at 75 ° C for 60 min and then dried at 150 ° C for 30 min;
  • Steps (3) to (6) are cycled 5 times;
  • the aluminum shell was placed, sealed with a rubber stopper, and aged to obtain a solid electrolyte aluminum electrolytic capacitor.
  • the method of aging is to put the product into the environment of 110 ° C, apply 0.2 times of rated voltage, 80 min, then apply 0.5 times of rated voltage for 60 min, then apply 0.8 times of rated voltage for 40 min, then apply 1.0 times of rated voltage for 20 min, then apply 1.2 times.
  • the rated voltage can be 20min.
  • Table 5 is a performance test of the capacitor prepared in Example 5.
  • the capacitor is manufactured by:
  • JCC anode foil model number 110LJB22B-33VF-58.4 ⁇ F, width 17mm, length 391mm
  • Nanofoil cathode foil model NF3000, width 17mm, length 421mm
  • electrolytic paper NKK, RTZ3040 width 20mm, made into a capacitor size of 16V3300 ⁇ F, size ⁇ 16*26mm.
  • the anode foil and the cathode foil are wound together into a core package by electrolytic paper, the anode of the core package is welded to the iron bar, the core package is immersed in the chemical conversion liquid, and a voltage of 365 V is applied according to the voltage of the positive foil in the phosphoric acid chemical conversion liquid. After formation, the core package is immersed in 70 ° C pure water for 30 minutes to remove the residual components in the chemical solution, and then dried at 75 ° C for 60 min and then dried at 150 ° C for 30 min;
  • the core package is immersed in the dispersion A, the vacuum is broken, and the compressed air is introduced to pressurize to 0.5 MPa, the impregnation time is 5 min; the core package is taken out, and it is dried at 85 ° C for 60 min;
  • Steps (3) to (5) are cycled 5 times;
  • the aluminum shell was placed, sealed with a rubber stopper, and aged to obtain a solid electrolyte aluminum electrolytic capacitor.
  • the method of aging is to put the product into the environment of 110 ° C, apply 0.2 times of rated voltage, 80 min, then apply 0.5 times of rated voltage for 60 min, then apply 0.8 times of rated voltage for 40 min, then apply 1.0 times of rated voltage for 20 min, then apply 1.2 times.
  • the rated voltage can be 20min.
  • Table 6 shows the performance test of the capacitor prepared in Example 6.
  • Example 20 capacitors were fabricated and analyzed similarly to Example 5, except that this example used JCC anode foil (model: HGF110J16-365VF-1.33 ⁇ F, width 7.5mm, length 192mm), Nanofoil cathode foil (model NF3000) The width is 7.5 mm, the length is 212 mm), and the anode foil and the cathode foil are wound into a core package by an electrolytic paper having a width of 15 mm and model Asahi Kasel ADS040060, and a capacitor having a size of 200 V 15 uF and a size of ⁇ 10 * 12 mm is formed.
  • Table 7 The results of the analysis are shown in Table 7.
  • Table 7 shows the performance test of the capacitor prepared in Example 7.
  • Example 20 capacitors were fabricated and analyzed similarly to Example 5, except that JCC anode foil (model HGF110J16-365VF-1.33 ⁇ F, width 13mm, length 302mm) and Nanofoil cathode foil (model NF3000 width 13mm) were used.
  • the length is 327 mm
  • the anode foil and the cathode foil are wound into a core package by an electrolytic paper having a width of 15 mm and model number Asahi Kasel ADS040060, and a capacitor having a size of 200 V47 uF and a size of ⁇ 13*20 mm is prepared, and the analysis results are shown in Table 8. .
  • Table 8 shows the performance test of the capacitor prepared in Example 8.
  • Table 9 shows the performance test of the capacitor prepared in Example 9.
  • Table 10 is a performance test of the capacitor prepared in Example 10.
  • the solid electrolyte used in this embodiment is a mixture of a conductive polymer and a conductive carbon material, wherein the conductive polymer is poly 3,4 ethylene dioxythiophene having a particle diameter of about 40 to 80 nm, preferably 60 nm; and the conductive carbon material is an average.
  • the capacitor is manufactured by:
  • JCC anode foil model number is HGF110J16-365VF-1.33 ⁇ F, width 17mm, length 491mm; Nanofoil cathode foil, model NF3000, width 17mm, length 521mm; electrolytic paper Asahi Kasel ADS040060, width is 20mm, the capacitor is made of 200V100 ⁇ F and the size is ⁇ 16*26mm.
  • the anode foil and the cathode foil are wound together into a core package by electrolytic paper, the anode of the core package is welded to the iron bar, the core package is immersed in the chemical conversion liquid, and a voltage of 365 V is applied according to the voltage of the positive foil in the phosphoric acid chemical conversion liquid. After formation, the core package is immersed in 40 ° C pure water for 30 minutes to remove the residual components in the chemical solution, and then dried at 50 ° C for 20 min and then dried at 160 ° C for 20 min;
  • Steps (3) to (6) are cycled 8 times;
  • the aluminum shell was placed, sealed with a rubber stopper, and aged to obtain a solid electrolyte aluminum electrolytic capacitor.
  • Table 11 is a performance test of the capacitor prepared in Example 1.
  • the conductive polymer used in this embodiment is poly 3,4 ethylene dioxythiophene having a particle diameter of about 40 to 80 nm, preferably 60 nm; the conductive carbon material is carbon nanotubes having an average length of 150 nm; and dispersion A is prepared separately. And dispersion C, wherein the concentrations of carbon nanotubes and poly 3,4 ethylene dioxythiophene are 5% and 2% by weight, respectively.
  • the capacitor is manufactured by:
  • JCC anode foil model number is HGF110J16-365VF-1.33 ⁇ F, width 17mm, length 491mm; Nanofoil cathode foil, model NF3000, width 17mm, length 521mm; electrolytic paper Asahi Kasel ADS040060, width is 20mm, the capacitor is made of 200V100 ⁇ F and the size is ⁇ 16*26mm.
  • the anode foil and the cathode foil are wound together into a core package by electrolytic paper, the anode of the core package is welded to the iron bar, the core package is immersed in the chemical conversion liquid, and a voltage of 365 V is applied according to the voltage of the positive foil in the phosphoric acid chemical conversion liquid. After formation, the core package is immersed in 40 ° C pure water for 30 minutes to remove the residual components in the chemical solution, and then dried at 50 ° C for 20 min and then dried at 160 ° C for 20 min;
  • the core package is retained in the dispersion A, vented to a normal pressure state, and the impregnation time is 10 min; the core package is taken out, dried at 85 ° C for 40 minutes, and then the core package is placed at a high temperature of 110 ° C for 60 minutes. , remove the core package;
  • the dried core package is immersed in the dispersion C, the impregnation time is 5 min; the core package is taken out, dried at 85 ° C for 20 min, and then the core package is placed at 165 ° C for 20 min at high temperature, and the core package is taken out;
  • Steps (3) to (8) are cycled 5 times;
  • the aluminum shell was placed, sealed with a rubber stopper, and aged to obtain a solid electrolyte aluminum electrolytic capacitor.
  • Table 12 is a performance test of the capacitor prepared in Example 12.
  • the conductive polymer used in this embodiment is poly 3,4 ethylene dioxythiophene having a particle diameter of about 40 to 80 nm, preferably 60 nm; the conductive carbon material is carbon nanotubes having an average size of 100 nm; and dispersion A is prepared separately. And dispersion C, wherein the concentrations of carbon nanotubes and poly 3,4 ethylene dioxythiophene are 0.5% and 2.5% by weight, respectively.
  • the capacitor is manufactured by:
  • JCC anode foil model number is HGF110J16-365VF-1.33 ⁇ F, width 17mm, length 491mm; Nanofoil cathode foil, model NF3000, width 17mm, length 521mm; electrolytic paper Asahi Kasel ADS040060, width is 20mm, the capacitor is made of 200V100 ⁇ F and the size is ⁇ 16*26mm.
  • the anode foil and the cathode foil are wound together into a core package by electrolytic paper, the anode of the core package is welded to the iron bar, the core package is immersed in the chemical conversion liquid, and a voltage of 365 V is applied according to the voltage of the positive foil in the phosphoric acid chemical conversion liquid. After formation, the core package is immersed in 40 ° C pure water for 30 minutes to remove the residual components in the chemical solution, and then dried at 50 ° C for 20 min and then dried at 160 ° C for 20 min;
  • the core package was removed from the dispersion A, and vacuumed to a vacuum of 970 Pa, and the core package was dipped into the dispersion B, and the impregnation time was 8 min;
  • Steps (4) to (8) are cycled 5 times;
  • Table 13 is a performance test of the capacitor prepared in Example 13.
  • Table 14 shows the performance test of the capacitor prepared in Comparative Example 1.
  • Table 15 shows the performance test of the capacitor prepared in Comparative Example 2.
  • the specification of the capacitor is 16V 3300uF 18*36.5mm, and the specific manufacturing method is as follows:
  • Anodized aluminum foil and cathode foil are wound together into a core package by electrolytic paper;
  • the treatment time is 10 minutes;
  • the core package is placed in a monomer for impregnation.
  • the impregnation time is 6 min. After completion, the solvent is removed;
  • the core package is placed in an oxidizing agent for impregnation. When impregnating, the core package is all below the impregnation liquid surface.
  • the impregnation method is to first immerse the core which is internal pressure in the oxidant for 2 minutes, and then remove the oxidant and pump. Vacuum to a vacuum of 90KPa or less, keep 2min, after the time is up, deflate at atmospheric pressure, and pass compressed air to a pressure of 3atm, immersed in oxidant for 5min, time to complete impregnation;
  • Two-stage polymerization of the impregnated core package first, low temperature polymerization, polymerization temperature 50 ⁇ 10 ° C, polymerization time 200 ⁇ 10 min; second, high temperature polymerization, polymerization temperature 150 ⁇ 10 ° C, polymerization time 100 ⁇ 10 min ;
  • Aging treatment and test sorting firstly apply a voltage of 0.5 times, 1 time, 1.2 times of the rated voltage to one pole of the capacitor, and then apply the rated voltage to the other pole of the capacitor respectively.
  • the aging treatment was performed at a voltage of 0.5 times, 1 time, and 1.2 times.
  • the comparative example adopts a solvent type solvent which is a monomer and an oxidizing agent.
  • a solvent type solvent which is a monomer and an oxidizing agent.
  • the surface tension of the solvent used is small, it can penetrate into the micropores of the formed foil, and a conductive polymer is formed in the micropores, and the micropores are formed.
  • the anode foil, the cathode foil, and the electrolytic paper used in the method for manufacturing the capacitor and the specifications are the same as in the fifth embodiment, and the capacitor is made to have a specification of 200 V 100 ⁇ F and a size of ⁇ 16 * 26 mm.
  • the specific manufacturing method is as follows:
  • Anodized aluminum foil and cathode foil are wound together into a core package by electrolytic paper;
  • the core package is placed at 300 ° C for carbonization to remove ash; the core package is placed in an aqueous solution of 7% ammonium diphosphate, and a voltage of 9 V is applied for 15 minutes to repair the damaged oxide film;
  • the oxidant p-toluenesulfonic acid iron is formulated into a 40-60% alcohol solution, and the core package treated in the step (2) is immersed in the above alcohol solution for 3-6 minutes, and the core package is taken out and placed at 60-70 ° C. Drying to remove the alcohol solution;
  • the monomer 3,4 ethylene dioxythiophene is formulated into an alcohol solution of 40 to 55%, and the core impregnated with the oxidizing agent and dried is immersed in an alcohol solution of the monomer for 2 to 4 minutes, and the core package is taken out. Drying at 60-70 ° C to remove the alcohol solution; heating to 110 ⁇ 120 ° C to cause polymerization to form a conductive polymer conductive layer;
  • Table 16 shows the performance test of the capacitor prepared in Comparative Example 4.
  • the electrolyte in the dispersion A when the core package is immersed in the dispersion A under the conditions of a combination of atmospheric pressure, vacuum and pressure, the electrolyte in the dispersion A can be more stably formed on the surface of the foil.
  • Impregnating solvent is beneficial to the next absorption of the impregnation liquid, and can obtain a lower ESR high-pressure solid electrolyte aluminum electrolytic capacitor, which can improve the extraction rate, reduce the loss and improve the consistency of the product; especially (vacuum impregnation + low temperature drying) ⁇ (Pressure impregnation + low temperature drying) ⁇ (atmospheric pressure impregnation + low temperature drying + high temperature drying) cycle impregnation process, more conducive to the next absorption of conductive polymer in the impregnation liquid, can obtain lower ESR, core immersion It is more transparent and more complete, and a stable conductive polymer layer is obtained.
  • the capacitor is impregnated in a vacuum state, and its main function is to extract the gas in the electrolytic paper, the surface of the foil, and the micropores of the foil, thereby vacating the adsorption of the dispersion A, and adsorbing more dispersion A. If there are bubbles on the surface of the foil, the adsorption of the dispersion A is prevented, and the integrity of the film formed on the surface of the foil after the drying of the dispersion A is affected, thereby affecting the performance of the product. At the same time, the vacuum can take away the bubbles in the dispersion A, thereby improving the penetration effect of the dispersion A.
  • the core immersed in the dispersion A After vacuum impregnation, it enters the normal pressure state, mainly by means of the pressure of the gas, and the core immersed in the dispersion A is further infiltrated under an atmospheric pressure condition.
  • the principle of the pressure is the same, that is, it is larger than the vacuum.
  • the pressure difference causes the core immersed in the dispersion A to be more thoroughly immersed and adsorb more dispersion A.
  • the combination of three different pressure states of vacuum, normal pressure and pressurization can have different pressures in different states, and the pressure is increased step by step to make the core package more permeable and more permeable.
  • the dispersion A passes through a longer path and is less suitable for penetration. It is difficult to achieve core impregnation effect by combining vacuum and atmospheric pressure or combining pressure and atmospheric pressure. It also has a certain impact on its performance.
  • Example 11 Example 12 and Example 13 are carbon materials having a stronger conductivity in the conductive polymer electrolyte to increase the conductivity of the conductive polymer.
  • ESR series equivalent resistance
  • the loss of the product will be slightly reduced.
  • Different ways of adding will have minor differences in the product, such as concentration, and there will be minor differences in the order of the impregnation, which may be optimized through multiple trials.
  • Example 5 since no carbon material increases the conductivity, the resistance of the series without the conductive carbon material is increased, and the loss is slightly increased.
  • the present invention also carries out process optimization and improvement, and the following describes the orthogonal optimization experiment.
  • the orthogonal optimization experiment is carried out for 7 factors and three levels, and 18 experiments are performed. After the aging is finished, 20 samples are respectively taken for testing, and the test results are average values, as shown in Table 17.
  • Table 17 shows the factors and level and performance tests of orthogonal optimization experiments.
  • the vacuum is not as high as possible. Too low may cause the gas in the core package to be unclean, which may result in the dispersion of the dispersion A being incomplete; the degree of vacuum is too high, resulting in the dispersion A. The loss of water, resulting in increased viscosity, will also affect the actual impregnation effect.
  • the vacuum impregnation time also has the same production problem in the impregnation. The time is too short, the impregnation is not sufficient, and the growth time can improve the impregnation effect, but after a certain period of time, the effect of the improvement is not obvious, and the time is too long, resulting in dispersion.
  • the bulk A has a high viscosity, which causes no impregnation in the next cycle.
  • the pressure of the impregnation impregnation is obviously improved for the impregnation effect, the pressure impregnation time is increased, and the impregnation effect is also improved.
  • the safety is not increased, and the pressure is not increased.
  • the purpose of low-temperature drying is to let the water in the dispersion slowly discharge out of the core package. If the temperature is too high until the water is boiled, the formation of the polymer film on the surface of the foil will be affected. If the temperature is too low, the discharge speed will be affected. An increase in time will improve the effect of water discharge, but too long will not significantly increase the effect and result in reduced production efficiency.
  • the purpose of high-temperature drying is to further remove the water in the core package. The temperature selection is limited by high preparation, and the high-temperature drying time should also be selected for a suitable time. If it is too long, it will have no effect and will cause some damage to the product.

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Abstract

本发明公开了一种固体电解质铝电解电容器，包括铝壳及设置在所述铝壳内的芯包，所述芯包包括阳极化成铝箔、阴极箔、介于所述阳极化成铝箔与阴极箔之间的电解纸和固体电解质，所述固体电解质包括导电聚合物和导电碳材料。该固体电解质铝电解电容器具有优异ESR性能，其固体电解质为导电聚合物和导电碳材料，可解决的高温度下导电聚合物电阻显著增大问题及性能低下等问题。本发明还公开了该固体电解质铝电解电容器的制造方法。该种制造方法可以获得较低ESR值、较高耐压值的固态电容器，同时获得较低的漏电流，也获得了较好的批量一致性。

Description

一种固体电解质铝电解电容器及其制造方法 技术领域
本发明涉及电解电容器的制备技术领域，具体涉及一种固体电解质铝电解电容器及其制造方法。
背景技术
固体电解电容器相比较普通的液体电解电容器，其电性能很突出，具有低等效串联电阻(ESR)，高耐纹波电流，使用寿命长，性能稳定等优点。随着电子产品的不断升级换代，其功能及性能的不断提高，对电容器的高频特性要求也越来越高，人们通过各种不同途径降低固体电解电容器的ESR，以满足电容器的高频特性。
然而固态电容虽然有其无可替代的优点，但由于现行的工艺方式存在两大问题，一是产品的电压不能太高，通常为35V以下，一个是漏电流较大，通常达到0.05CV.这些问题产生的原因就是因为固态电容在生产过程中，通常是采用溶剂将单体与氧化剂溶解，通过含浸的方式进入芯包，然后给予一定的条件让其进行聚合生成能导电的固体电解质。这种生产工艺存在两个缺点，一是氧化剂本身具有很强的酸性，对正极箔的氧化膜有较大的破坏作用，大大降低了正极箔原有的电压值，另一个是因为单体与氧化剂是溶解在溶剂中含浸到芯包里，因为溶剂与电极正箔的浸润性良好，故将氧化剂与单体带到阳极箔的腐蚀的微孔中，因为微孔是化成时生成氧化膜比较薄弱的地方，加之固体电解质没有修复能力，这个地方的耐压较低，当通以一定的电压后，会产生较大的漏电流使产品失效。
为了解决这个问题，技术解决方案是将导电聚合物在水中聚合，形成水的分散体，然后通过含浸的形式浸入到芯包中，这样作成的电容，由于没有氧化剂对箔的伤害，使产品的耐压有所增加，同时在水中分散的聚合物，聚合物分子有一定的尺寸，由于在水中分散，水的浸润性比一般溶剂要差，这样可以确保正极箔的微孔中浸入导电聚合物，这个耐压比较薄弱的地方因没有聚合物没有办法形成较大的漏电，故可以大幅提高产品的耐压。
现行的技术中，没有考虑水的浸润性差的问题，采用较为普通的含浸方式，故在产品的引出率方面，以及做更大尺寸，例如超过Φ10*12mm尺寸较为困难，或一致性较差。
发明内容
为了克服了现有技术中的缺点，本发明提供了一种具有优异ESR性能的固体电解质铝电解电容器，其固体电解质为导电聚合物和导电碳材料，可解决的高温度下导电聚合物电阻显著增大问题及性能低下等问题。本发明还提供了该固体电解质铝电解电容器的制造方法，该方法主要是通过在不同压力环境下含浸芯包来解决微孔中不能浸到或浸到极少量的导电聚合物和导电碳材料的问题，不仅实现耐压的提高，还通过优化含浸工艺，确保在可含浸的区域有较多的固体电解质，且分布均匀。该种制造方法可以获得较低ESR值、较高耐压值的固态电容器，同时获得较低的漏电流，同 时也获得了较好的批量一致性。
本发明所要解决的技术问题通过以下技术方案予以实现：
本发明提供了一种固体电解质铝电解电容器，包括铝壳及设置在所述铝壳内的芯包，所述芯包包括阳极化成铝箔、阴极箔、介于所述阳极化成铝箔与阴极箔之间的电解纸和固体电解质，所述固体电解质包括导电聚合物和导电碳材料。
优选地，所述导电聚合物为聚3,4乙烯二氧噻吩。
优选地，所述导电碳材料为碳纳米材料或碳纳米复合材料。
本发明还提供了所述固体电解质铝电解电容器的制造方法，包括：
(1)将电容器的芯包焊于铁条上，施加电压进行化成，化成后进行清洗并干燥；
(2)将干燥后的芯包浸入分散体B中，含浸时间1～30min；
(3)将芯包移出分散体B，抽真空后再将芯包浸入分散体B，含浸时间1～10min；
(4)将芯包保留在分散体B中，破真空，再加压，含浸时间1～10min；
(5)将芯包保留在分散体B中，放气至常压，含浸时间1～10min；
(6)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
(7)步骤(3)至(6)至少重复一次；
(8)入壳封口，老化处理获得固体电解质铝电解电容器；其中，
所述分散体B为含导电聚合物和导电碳材料的分散体。
本发明提供了另一种固体电解质铝电解电容器的制造方法，包括：
(1)将电容器的芯包焊于铁条上，施加电压进行化成，化成后进行清洗并干燥；
(2)将干燥后的芯包浸入分散体A中，含浸时间1～30min；
(3)将芯包移出分散体A，抽真空后再将芯包浸入分散体A，含浸时间1～10min；
(4)将芯包保留在分散体A中，破真空，再加压，含浸时间1～10min；
(5)将芯包保留在分散体A中，放气至常压，含浸时间1～10min；
(6)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
(7)将干燥后的芯包浸入分散体C中，含浸时间1～30min；
(8)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
(9)步骤(3)至(8)至少重复一次；
(10)入壳封口，老化处理获得固体电解质铝电解电容器；其中，
所述分散体A和分散体C分别为含导电聚合物的分散体和含导电碳材料的分散体。
本发明又提供了一种固体电解质铝电解电容器的制造方法，包括：
(1)将电容器的芯包焊于铁条上，施加电压进行化成，化成后进行清洗并干燥；
(2)将干燥后的芯包浸入分散体C中，含浸时间1～30min；
(3)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
(4)将干燥后的芯包浸入分散体A中，含浸时间1～30min；
(5)将芯包移出分散体A，抽真空后再将芯包浸入分散体A，含浸时间1～10min；
(6)将芯包保留在分散体A中，破真空，再加压，含浸时间1～10min；
(7)将芯包保留在分散体A中，放气至常压，含浸时间1～10min；
(8)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
(9)步骤(5)至(8)至少重复一次；
(10)入壳封口，老化处理获得固体电解质铝电解电容器；其中，
所述分散体A和分散体C分别为含导电聚合物的分散体和含导电碳材料的分散体。
优选地，所述步骤(3)中抽真空的真空度为700～970Pa。
优选地，所述步骤(4)中加压为通入压缩空气，加压至0.1～0.6MPa。
优选地，所述步骤(9)为步骤(3)至(8)重复5次。
优选地，所述导电碳材料为碳纳米材料或碳纳米复合材料；所述碳纳米材料为碳纳米管或石墨烯。
与现有技术相比，本发明具有如下有益效果：
(1)本发明采用常压、真空、加压多种压力环境结合的条件下将芯包浸入分散体时，分散体中的电解质能够更充分在箔的表面生成稳定的导电高分子层和导电碳层，提高电容器电性能；同时，导电聚合物和导电碳材料作为固体电解质，能够有效提高固体电解质铝电解电容器的耐电压值；
(2)本发明采用多次重复含浸步骤，热处理后除去含浸溶剂的芯包，有利于下次对含浸液的吸收，可以获得更低ESR的固体电解质铝电解电容器，提高引出率，降低损耗同时可以提高产品的一致性，特别是对于大尺寸的电容器，例如大于10*12mm尺寸；该制造方法进一步提高了生产效率，便于规模化、自动化生产；
(3)与其他固态电解电容器相比，该电容器是以导电碳材料复合导电聚合物为固体电解质，降低了固体电解质电阻，使得该电容器的低等效串联电阻更小。
(4)本发明解决了铝阴极与固体电解质接触时电阻较大等技术难题，本发明提供的固体电解电容器具有高的稳定性和可靠性、低的等效串联电阻以及小漏电流等优点，可长时间在高低温环境下工作而保持性能稳定。
具体实施方式
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
本发明提供了一种固体电解质铝电解电容器，包括铝壳及设置在所述铝壳内的芯包，所述芯包连接正负极端子，所述正负极端子外表面镀有镀银层；所述芯包外部设置有胶盖或橡胶塞。所述芯包包括阳极化成铝箔、阴极箔、介于所述阳极化成铝箔与阴极箔之间的电解纸和固体电解质，所述 固体电解质可以是导电聚合物，还可以是导电聚合物和导电碳材料的复合材料。所述固体电解质通过含浸导电聚合物和/或导电碳材料分散体聚合获得。
优选但不限定，所述阳极化成铝箔采用日本蓄电器工业株式会社生产的JCC阳极箔，其型号为HGF110J16-365VF-1.33μF，宽度为17mm，长度为491mm；所述阴极箔采用Nanofoil阴极箔，其型号为NF3000，宽度为17mm，长度为521mm；所述电解纸为Asahi Kasel DS040060，其宽度为20mm。
优选但不限定，所述固体电解质可以是导电聚合物；还可以是导电聚合物和导电碳材料的物理混合物或组合物，可通过导电聚合物和导电碳材料相互混合成固体电解质，还可通过导电聚合物与导电碳材料相互层叠成固体电解质，但不局限于此。
本发明用到的分散体A和分散体C分别为含导电聚合物的分散体和含导电碳材料的分散体；分散体B为含导电聚合物和导电碳材料的分散体。
优选但不限定，所述导电聚合物为聚苯胺和/或聚吡咯和/或聚噻吩和/或聚3,4乙烯二氧噻吩。所述导电聚合物分散体，即分散体A具体制备方法见中国专利CN 101309949B，在此不再赘述，其中所述导电聚合物的浓度优选但不仅限于为2～3％(重量百分比)。
优选但不限定，所述导电碳材料为碳纳米材料或碳纳米复合材料，所述导电碳材料的尺寸优选石墨烯粒径为小于200nm，碳纳米管长度为2～200nm。所述碳纳米材料为碳纳米管或石墨烯；所述碳纳米复合材料中的活性材料为如下材料中的一种或多种：导电聚合物、金属氧化物、导电聚合物之间的混合物、导电聚合物和金属氧化物之间的混合物、金属氧化物之间的混合物、导电聚合物之间的复合物、导电聚合物和金属氧化物之间的复合物、金属氧化物之间的复合物。
优选但不限定，将乙醇溶液放入高速剪切机中，剪切速度为2.0万转/分钟，将石黑烯或碳纳米管或碳纳米复合材料，慢慢加入搅拌中的酒精溶液中，搅拌时间控制在30min以上，配制成含导电碳材料分散体，即分散体C。该含导电碳材料酒精分散液的浓度控制在0.5～5％(重量百分比)之间，还可适量加些分散剂，如十二烷基硫酸钠(SDS)，十二烷基苯磺酸钠(SDBS)。
优选但不限定，将乙醇溶液放入高速剪切机中，剪切速度为2.0万转/分钟，将石黑烯或碳纳米管或碳纳米复合材料，慢慢加入搅拌中的酒精溶液中，导电碳材料浓度控制在0.5～5％(重量百分比)之间，随后加入导电聚合物，导电聚合物浓度可控制在2～3％(重量百分比)之间，搅拌时间控制在30min以上，配制成含导电碳材料和导电聚合物的分散体，即分散体B，还可适量加些分散剂，如十二烷基硫酸钠(SDS)，十二烷基苯磺酸钠(SDBS)。
本发明提供了一种固体电解质铝电解电容器的制造方法，所述固体电解质为导电聚合物；该制造方法具体包括：
(1)阳极化成铝箔与阴极箔之间用电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加一定电压进行化成，化成时间不小于20min，所述化成液可以是磷酸系化成液、硼酸系化成液或已二酸铵系化成液；
化成后将芯包浸于40～100℃纯水浸泡30～60min，除去化成液中残留的成份，再进行干燥。干燥分为两个步骤，第一步进行低温干燥，干燥的温度控在50～100℃，温度太低会影响干燥的效果，超过100℃干燥，液体在产品内会出现沸腾，会影响产品的特性。干燥的时间为20～100min，确保不能有在芯包内足够沸腾的水量。第二步干燥为110～200℃，确保残留的水份充分挥发，温度不宜太高，太高会伤害到导针出现熔锡现象，干燥时间为20～60min，时间太短会出现水份没有挥发干净，会影响下一次的含浸效果，以及产品的特性。时间太长，产品的阳极箔会出现劣化，影响产品的性能。
(2)将干燥后的芯包浸入分散体A中，含浸时间1～30min；
(3)将芯包移出分散体A，将芯包与分散体A一起抽真空至700～970Pa的真空状态，再将芯包浸入分散体A中，含浸时间1～10min；
(4)将芯包保留在分散体A中，破真空，通入压缩空气进行加压，加压至0.1～0.6MPa，含浸时间1～10min；
(5)将芯包保留在分散体A中，放气至常压状态，含浸时间1～10min；
(6)取出芯包，并将芯包置于50～100℃干燥20～60min(优选但不限定为85℃)，再将芯包置于110～200℃干燥20～60min(优选但不限定为150℃)，取出芯包；
(7)步骤(3)至(6)至少重复一次，优选但不限定为5次。所述分散体A中聚合物固含量较少，含浸一次引入的聚合物较少，会影响产品的一致性，ESR会稍高，损耗会大，同时太少，产品的寿命也不能保证，可根据实际需要进行多次重复含浸。
(8)装入铝壳，用橡胶塞封口，老化处理获得固体电解质铝电解电容器。老化的方法是将产品放入85～150℃的环境中，施加0.2倍额定电压，20～100min，再施加0.5倍额定电压20～100min，再施加0.8倍额定电压20～100min，再施加1.0倍额定电压20～100min，再施加1.2倍额定电压20～100min即可。
本发明还提供了另一种固体电解质铝电解电容器的制造方法，所述固体电解质为导电聚合物和导电碳材料。该制造方法具体包括：
(1)阳极化成铝箔与阴极箔之间用电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加一定电压进行化成，化成时间不小于20min；化成后将芯包浸于40～100℃纯水浸泡30～60min，除去化成液中残留的成份，再进行50～100℃低温干燥20～100min，然后110～200℃高温干燥20～60min；
(2)将干燥后的芯包浸入分散体B中，含浸时间1～30min；
(3)将芯包移出分散体B，将芯包与分散体一起抽真空至700～970Pa的真空状态，再将芯包浸入分散体B中，含浸时间1～10min；
(4)将芯包保留在分散体B中，破真空，通入压缩空气进行加压，加压至0.1～0.6MPa，含浸时间1～10min；
(5)将芯包保留在分散体B中，放气至常压状态，含浸时间1～10min；
(6)取出芯包，并将芯包置于50～100℃干燥20～60min(优选但不限定为85℃)，再将芯包置于110～200℃干燥20～60min(优选但不限定为150℃)，取出芯包；
(7)步骤(3)至(6)至少重复一次，优选但不限定为5次。
(8)装入铝壳，用橡胶塞封口，老化处理获得固体电解质铝电解电容器。
本发明还提供了一种固体电解质铝电解电容器的制造方法，所述固体电解质为导电聚合物和导电碳材料。该制造方法具体包括：
(1)阳极化成铝箔与阴极箔之间用电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加一定电压进行化成，化成时间不小于20min；化成后将芯包浸于40～100℃纯水浸泡30～60min，除去化成液中残留的成份，再进行50～100℃低温干燥20～100min，然后110～200℃高温干燥20～60min；
(2)将干燥后的芯包浸入分散体A中，含浸时间1～30min；
(3)将芯包移出分散体A，抽真空后再将芯包浸入分散体A，含浸时间1～10min；
(4)将芯包保留在分散体A中，破真空，再加压，含浸时间1～10min；
(5)将芯包保留在分散体A中，放气至常压，含浸时间1～10min；
(6)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
(7)将干燥后的芯包浸入分散体C中，含浸时间1～30min；
(8)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
(9)步骤(3)至(8)至少重复一次；
(10)入壳封口，老化处理获得固体电解质铝电解电容器。
本发明又提供了一种固体电解质铝电解电容器的制造方法，所述固体电解质为导电聚合物和导电碳材料。该制造方法具体包括：
(1)阳极化成铝箔与阴极箔之间用电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加一定电压进行化成，化成时间不小于20min；化成后将芯包浸于40～100℃纯水浸泡30～60min，除去化成液中残留的成份，再进行50～100℃低温干燥20～100min，然后110～200℃高温干燥20～60min；
(2)将干燥后的芯包浸入分散体B中，含浸时间1～30min；
(3)将芯包移出分散体B，抽真空后再将芯包浸入分散体B，含浸时间1～10min；
(4)将芯包保留在分散体B中，破真空，再加压，含浸时间1～10min；
(5)将芯包保留在分散体B中，放气至常压，含浸时间1～10min；
(6)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
(7)将干燥后的芯包浸入分散体C中，含浸时间1～30min；
(8)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
(9)步骤(3)至(8)至少重复一次；
(10)入壳封口，老化处理获得固体电解质铝电解电容器。
本发明所涉及的真空状态及加压状态均可在一个设备上实现也可两种设备，但优选一个设备上实现，同时所述芯包和分散体同时处于真空或常压或加压状态。
所述制造方法不仅适用于高压固体电解质铝电解电容器，也适用于钽、铌或钛等的固体电解质电容器。
以下结合具体实施例进行详细说明。
实施例1
本实施例所用到分散体A的导电聚合物为聚3,4乙烯二氧噻吩，其粒径约为40～80nm，优选60nm。电容器规格为200V100μF，尺寸Φ16*26mm。该电容器的制造方法为：
(1)JCC阳极箔(日本蓄电器工业株式会社生产)，其型号为HGF110J16-365VF-1.33μF，宽度为17mm，长度为491mm；Nanofoil阴极箔，其型号为NF3000，宽度为17mm，长度为521mm；电解纸Asahi Kasel ADS040060，宽度为20mm。所述阳极箔与阴极箔之间通过电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加365V电压在磷酸系化成液中化成20min；化成后将芯包浸于70℃纯水中浸泡30min以除去化成液中残留的成份，然后进行75℃低温干燥60min后再于150℃高温干燥30min；
(2)将干燥后的芯包浸入分散体A中，含浸时间为15min；
(3)将芯包移出分散体A，并抽真空至850Pa的真空状态，再将芯包浸入分散体A中，含浸时间为5min；
(4)取出芯包，将其置于85℃低温干燥60min，再将芯包置于150℃高温干燥30min，取出芯包；
(5)步骤(3)至(4)循环5次；
(6)装入铝壳，用橡胶塞封口，老化处理获得固体电解质铝电解电容器。老化的方法是将产品放入110℃的环境中，施加0.2倍额定电压，80min，再施加0.5倍额定电压60min，再施加0.8倍额定电压40min，再施加1.0倍额定电压20min，再施加1.2倍额定电压20min即可。
老化结束抽取20个进行测试，结果见表1。
表1为实施例1制得的电容器的性能测试
Figure PCTCN2015073533-appb-000001
Figure PCTCN2015073533-appb-000002
实施例2
类似于实施例1制造20个电容器并分析，电容器规格为200V100μF，尺寸Φ16*26mm，不同之处在于步骤(3)变为：将芯包保留在分散体A中，通入压缩空气进行加压至0.5MPa，含浸时间为5min，其他步骤及其顺序不变；其分析结果见表2。
表2为实施例2制得的电容器的性能测试
序号 CAP(uF) DF(％) ESR(mΩ)/100kHz LC(uA)/1min
1 93.82 3.51 17.30 18.00
2 93.99 3.85 18.40 15.00
3 94.23 3.45 15.60 33.00
4 93.84 3.77 16.50 15.00
5 94.98 3.85 17.10 13.00
6 93.68 3.11 17.60 10.00
7 94.31 3.50 16.50 10.00
8 91.48 4.93 17.40 7.00
9 92.90 4.28 15.80 8.00
10 92.51 3.41 16.30 6.00
11 94.91 3.20 16.50 20.00
12 93.43 3.58 17.40 7.00
13 92.65 3.05 16.20 14.00
14 91.21 3.40 16.40 12.00
15 93.98 3.71 16.90 4.00
16 94.36 3.29 16.80 9.00
17 93.96 4.01 16.90 8.00
18 92.82 3.09 18.50 8.00
19 93.13 3.07 17.50 7.00
20 92.47 3.16 17.80 11.00
MIN 91.21 3.05 15.60 4.00
MAX 94.98 4.93 18.50 33.00
AVE 93.43 3.56 16.97 11.75
实施例3
类似于实施例1制造20个电容器并分析，电容器规格为200V100μF，尺寸Φ16*26mm，不同之 处在于步骤(3)至步骤(4)之间增加了常压含浸步骤，该常压含浸步骤具体为：将芯包保留在分散体A中，破真空至常压状态，含浸时间为5min；其他步骤不变，其分析结果见表3。
表3为实施例3制得的电容器的性能测试
序号 CAP(uF) DF(％) ESR(mΩ)/100kHz LC(uA)/1min
1 96.16 2.87 14.50 56.00
2 97.58 3.22 14.30 31.70
3 94.38 2.97 13.80 17.30
4 96.03 2.90 14.30 15.00
5 94.05 2.87 15.20 13.30
6 97.31 3.37 13.20 12.80
7 97.49 2.87 14.70 11.10
8 97.45 2.90 13.30 9.00
9 97.59 2.81 15.80 9.80
10 95.68 2.92 13.60 9.00
11 96.89 2.83 14.10 32.00
12 97.52 2.93 13.60 20.20
13 97.60 3.23 13.20 30.00
14 96.80 2.77 14.40 15.60
15 95.52 3.06 13.80 12.00
16 96.96 3.11 13.70 13.30
17 97.55 2.98 13.90 14.00
18 95.94 2.94 14.24 9.20
19 97.48 3.97 15.66 9.00
20 98.08 2.97 13.05 8.30
MIN 94.05 2.77 13.05 8.30
MAX 98.08 3.97 15.80 56.00
AVE 96.70 3.02 14.12 17.43
实施例4
类似于实施例2制造20个电容器并分析，电容器规格为200V100μF，尺寸Φ16*26mm，不同之处在于步骤(3)至步骤(4)之间增加了常压含浸步骤，该常压含浸步骤具体为：将芯包保留在分散体A中，放气至常压状态，含浸时间为5min；其他步骤不变，其分析结果见表4。
表4为实施例4制得的电容器的性能测试
Figure PCTCN2015073533-appb-000003
Figure PCTCN2015073533-appb-000004
实施例5
该电容器的制造方法为：
(1)JCC阳极箔，其型号为HGF110J16-365VF-1.33μF，宽度为17mm，长度为491mm；Nanofoil阴极箔，其型号为NF3000，宽度为17mm，长度为521mm；电解纸Asahi Kasel ADS040060，宽度为20mm，作成电容器规格为200V100μF，尺寸Φ16*26mm。所述阳极箔与阴极箔之间通过电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加365V电压在磷酸系化成液中化成20min；化成后将芯包浸于70℃纯水中浸泡30min以除去化成液中残留的成份，然后进行75℃低温干燥60min后再于150℃高温干燥30min；
(2)将干燥后的芯包浸入分散体A中，含浸时间为15min；
(3)将芯包移出分散体A，并抽真空至850Pa的真空状态，再将芯包浸入分散体A中，含浸时间为5min；
(4)将芯包保留在分散体A中，破真空，并通入压缩空气进行加压至0.5MPa，含浸时间为5min；
(5)将芯包保留在分散体A中，放气至常压状态，含浸时间为5min；
(6)取出芯包，将其置于85℃低温干燥60min，再将芯包置于150℃高温干燥30min，取出芯包；
(7)步骤(3)至(6)循环5次；
(8)装入铝壳，用橡胶塞封口，老化处理获得固体电解质铝电解电容器。老化的方法是将产品放入110℃的环境中，施加0.2倍额定电压，80min，再施加0.5倍额定电压60min，再施加0.8倍额定电压40min，再施加1.0倍额定电压20min，再施加1.2倍额定电压20min即可。
老化结束抽取20个进行测试，结果见表5。
表5为实施例5制得的电容器的性能测试
Figure PCTCN2015073533-appb-000005
Figure PCTCN2015073533-appb-000006
实施例6
该电容器的制造方法为：
(1)JCC阳极箔，其型号为110LJB22B-33VF-58.4μF，宽度为17mm，长度为391mm；Nanofoil阴极箔，其型号为NF3000，宽度为17mm，长度为421mm；电解纸NKK,RTZ3040，宽度为20mm，作成电容器规格为16V3300μF，尺寸Φ16*26mm。所述阳极箔与阴极箔之间通过电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加365V电压在磷酸系化成液中化成20min；化成后将芯包浸于70℃纯水中浸泡30min以除去化成液中残留的成份，然后进行75℃低温干燥60min后再于150℃高温干燥30min；
(2)将干燥后的芯包浸入分散体A中，含浸时间为15min；
(3)将芯包移出分散体A，并抽真空至850Pa的真空状态，再将芯包浸入分散体A中，含浸时间为5min；取出芯包，将其置于85℃低温干燥60min；
(4)将芯包浸在分散体A中，破真空，并通入压缩空气进行加压至0.5MPa，含浸时间为5min；取出芯包，将其置于85℃低温干燥60min；
(5)将芯包浸在分散体A中，放气至常压状态，含浸时间为5min；取出芯包，将其置于85℃低温干燥60min，再将芯包置于150℃高温干燥30min，取出芯包；
(6)步骤(3)至(5)循环5次；
(7)装入铝壳，用橡胶塞封口，老化处理获得固体电解质铝电解电容器。老化的方法是将产品放入110℃的环境中，施加0.2倍额定电压，80min，再施加0.5倍额定电压60min，再施加0.8倍额定电压40min，再施加1.0倍额定电压20min，再施加1.2倍额定电压20min即可。
老化结束抽取20个进行测试，结果见表6。
表6为实施例6制得的电容器的性能测试
Figure PCTCN2015073533-appb-000007
Figure PCTCN2015073533-appb-000008
实施例7
类似于实施例5制造20个电容器并分析，不同之处在于本实施例采用JCC阳极箔(型号为HGF110J16-365VF-1.33μF，宽度为7.5mm，长度为192mm)、Nanofoil阴极箔(型号为NF3000宽度为7.5mm，长度为212mm)且阳极箔与阴极箔之间通过宽度为15mm型号为Asahi Kasel ADS040060的电解纸一起卷绕成芯包，作成规格为200V15uF，尺寸为Φ10*12mm的电容器，其分析结果见表7。
表7为实施例7制得的电容器的性能测试
Figure PCTCN2015073533-appb-000009
Figure PCTCN2015073533-appb-000010
实施例8
类似于实施例5制造20个电容器并分析，不同之处在于采用JCC阳极箔(型号为HGF110J16-365VF-1.33μF，宽度为13mm，长度为302mm)、Nanofoil阴极箔(型号为NF3000宽度为13mm，长度为327mm)，且阳极箔与阴极箔之间通过宽度为15mm型号为Asahi Kasel ADS040060的电解纸一起卷绕成芯包，作成规格200V47uF，尺寸为Φ13*20mm的电容器，其分析结果见表8。
表8为实施例8制得的电容器的性能测试
序号 CAP(uF) DF(％) ESR(mΩ)/100kHz LC(uA)/1min
1 46.74 3.30 17.90 13.20
2 47.07 3.38 18.10 7.40
3 46.99 3.22 17.80 6.90
4 47.11 2.91 16.90 9.10
5 47.21 3.01 16.60 13.90
6 46.52 2.74 17.20 8.80
7 47.66 2.88 18.30 6.50
8 45.65 2.59 17.60 6.70
9 47.66 2.80 16.70 13.80
10 46.63 3.00 17.50 7.90
11 46.98 3.40 17.50 11.70
12 45.78 3.40 17.80 7.80
13 46.80 3.00 17.30 11.10
14 46.90 3.00 17.00 6.20
15 46.29 3.20 18.30 7.50
16 45.74 2.60 17.60 8.70
17 46.05 2.80 16.60 18.20
18 46.16 2.60 18.00 5.90
19 46.28 2.60 17.40 7.40
20 47.00 2.97 18.10 18.00
MIN 45.65 2.59 16.60 5.90
MAX 47.66 3.40 18.30 18.20
AVE 46.66 2.97 17.51 9.84
实施例9
类似于实施例5制造20个电容器并分析，作成电容器规格为200V100μF，尺寸Φ16*26mm，不同之处在于本实施例所用到的导电聚合物粒径约为30～50nm，其分析结果见表9。
表9为实施例9制得的电容器的性能测试
Figure PCTCN2015073533-appb-000011
Figure PCTCN2015073533-appb-000012
实施例10
类似于实施例5制造20个电容器并分析，作成电容器规格为200V100μF，尺寸Φ16*26mm，不同之处在于本实施例所用到的导电聚合物粒径约为70～90nm，其分析结果见表10。
表10为实施例10制得的电容器的性能测试
序号 CAP(uF) DF(％) ESR(mΩ)/100kHz LC(uA)/1min
1 102.21 1.62 20.00 5.80
2 101.82 1.91 19.80 4.80
3 101.68 1.78 20.70 4.20
4 102.10 1.80 18.90 6.20
5 102.94 1.93 18.10 5.50
6 102.64 1.74 19.60 5.80
7 102.75 2.03 21.60 4.80
8 101.52 1.77 18.90 6.20
9 102.57 1.87 18.20 6.00
10 102.91 2.18 17.20 6.00
11 100.16 1.75 19.70 4.60
12 101.70 1.89 18.90 4.20
13 101.91 2.01 19.40 6.90
14 101.77 2.11 18.90 5.90
15 101.39 1.74 18.80 4.70
16 100.44 1.86 19.60 4.50
17 100.25 1.85 20.50 5.90
18 102.52 2.22 18.60 4.20
19 103.01 1.85 19.00 7.30
20 102.58 2.21 21.50 4.60
MIN 100.16 1.62 17.20 4.20
MAX 103.01 2.22 21.60 7.30
AVE 101.94 1.91 19.40 5.41
实施例11
本实施例所用到的固体电解质为导电聚合物和导电碳材料的混合物，其中导电聚合物为聚3,4乙烯二氧噻吩，其粒径约为40～80nm，优选60nm；导电碳材料为平均粒径为150nm的石墨烯；并将聚3,4乙烯二氧噻吩与石墨烯按重量百分比为1:1制备成分散体B，其中石墨烯和聚3,4乙烯二氧噻吩的浓度分别为重量百分比3％和3％。该电容器的制造方法为：
(1)JCC阳极箔，其型号为HGF110J16-365VF-1.33μF，宽度为17mm，长度为491mm；Nanofoil阴极箔，其型号为NF3000，宽度为17mm，长度为521mm；电解纸Asahi Kasel ADS040060，宽度为20mm，作成电容器规格为200V100μF，尺寸Φ16*26mm。所述阳极箔与阴极箔之间通过电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加365V电压在磷酸系化成液中化成20min；化成后将芯包浸于40℃纯水中浸泡30min以除去化成液中残留的成份，然后进行50℃低温干燥20min后再于160℃高温干燥20min；
(2)将干燥后的芯包浸入分散体B中，含浸时间为1min；
(3)将芯包移出分散体B，并抽真空至700Pa的真空状态，再将芯包浸入分散体B中，含浸时间为5min；
(4)将芯包保留在分散体B中，破真空，并通入压缩空气进行加压至0.4MPa，含浸时间为5min；
(5)将芯包保留在分散体B中，放气至常压状态，含浸时间为5min；
(6)取出芯包，将其置于65℃低温干燥60min，再将芯包置于150℃高温干燥40min，取出芯包；
(7)步骤(3)至(6)循环8次；
(8)装入铝壳，用橡胶塞封口，老化处理获得固体电解质铝电解电容器。
老化结束抽取20个进行测试，结果见表11。
表11为实施例1制得的电容器的性能测试
Figure PCTCN2015073533-appb-000013
Figure PCTCN2015073533-appb-000014
实施例12
本实施例所用到的导电聚合物为聚3,4乙烯二氧噻吩，其粒径约为40～80nm，优选60nm；导电碳材料为平均长度为150nm的碳纳米管；并分别制备分散体A和分散体C，其中碳纳米管和聚3,4乙烯二氧噻吩的浓度分别为重量百分比5％和2％。该电容器的制造方法为：
(1)JCC阳极箔，其型号为HGF110J16-365VF-1.33μF，宽度为17mm，长度为491mm；Nanofoil阴极箔，其型号为NF3000，宽度为17mm，长度为521mm；电解纸Asahi Kasel ADS040060，宽度为20mm，作成电容器规格为200V100μF，尺寸Φ16*26mm。所述阳极箔与阴极箔之间通过电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加365V电压在磷酸系化成液中化成20min；化成后将芯包浸于40℃纯水中浸泡30min以除去化成液中残留的成份，然后进行50℃低温干燥20min后再于160℃高温干燥20min；
(2)将干燥后的芯包浸入分散体A中，含浸时间为15min；
(3)将芯包移出分散体A，并抽真空至850Pa的真空状态，再将芯包浸入分散体B中，含浸时间为10min；
(4)将芯包保留在分散体A中，破真空，并通入压缩空气进行加压至0.1MPa，含浸时间为1min；
(5)将芯包保留在分散体A中，放气至常压状态，含浸时间为10min；取出芯包，将其置于85℃低温干燥40min，再将芯包置于110℃高温干燥60min，取出芯包；
(6)将干燥后的芯包浸入分散体C中，含浸时间为5min；取出芯包，将其置于85℃低温干燥20min，再将芯包置于165℃高温干燥20min，取出芯包；
(7)步骤(3)至(8)循环5次；
(8)装入铝壳，用橡胶塞封口，老化处理获得固体电解质铝电解电容器。
老化结束抽取20个进行测试，结果见表1。
表12为实施例12制得的电容器的性能测试
Figure PCTCN2015073533-appb-000015
Figure PCTCN2015073533-appb-000016
实施例13
本实施例所用到的导电聚合物为聚3,4乙烯二氧噻吩，其粒径约为40～80nm，优选60nm；导电碳材料为平均尺寸为100nm的碳纳米管；并分别制备分散体A和分散体C，其中碳纳米管和聚3,4乙烯二氧噻吩的浓度分别为重量百分比0.5％和2.5％。该电容器的制造方法为：
(1)JCC阳极箔，其型号为HGF110J16-365VF-1.33μF，宽度为17mm，长度为491mm；Nanofoil阴极箔，其型号为NF3000，宽度为17mm，长度为521mm；电解纸Asahi Kasel ADS040060，宽度为20mm，作成电容器规格为200V100μF，尺寸Φ16*26mm。所述阳极箔与阴极箔之间通过电解纸一起卷绕成芯包，将芯包的阳极焊接于铁条上，芯包浸入化成液，根据正箔的电压施加365V电压在磷酸系化成液中化成20min；化成后将芯包浸于40℃纯水中浸泡30min以除去化成液中残留的成份，然后进行50℃低温干燥20min后再于160℃高温干燥20min；
(2)将干燥后的芯包浸入分散体C中，含浸时间为30min；
(3)取出芯包，将其置于85℃低温干燥60min，再将芯包置于150℃高温干燥30min；
(4)将干燥后的芯包浸入分散体A中，含浸时间为15min；
(5)将芯包移出分散体A，并抽真空至970Pa的真空状态，再将芯包浸入分散体B中，含浸时间为8min；
(6)将芯包保留在分散体A中，破真空，并通入压缩空气进行加压至0.6MPa，含浸时间为10min；
(7)将芯包保留在分散体A中，放气至常压状态，含浸时间为1min；
(8)取出芯包，将其置于100℃低温干燥20min，再将芯包置于135℃高温干燥60min；
(9)步骤(4)至(8)循环5次；
(10)装入铝壳，用橡胶塞封口，老化处理获得固体电解质铝电解电容器。
老化结束抽取20个进行测试，结果见表13。
表13为实施例13制得的电容器的性能测试
Figure PCTCN2015073533-appb-000017
Figure PCTCN2015073533-appb-000018
对比例1
类似于实施例1作成电容器规格为200V100μF，尺寸Φ16*26mm的20个电容器并分析，不同之处在于去除步骤(3)，且步骤(2)至(4)循环5次，其分析结果见表14。
表14为对比例1制得的电容器的性能测试
Figure PCTCN2015073533-appb-000019
Figure PCTCN2015073533-appb-000020
对比例2
类似于实施例1作成电容器规格为200V100μF，尺寸Φ16*26mm的20个电容器并分析，不同之处在于去除步骤(3)和(5)，且步骤(2)含浸时间为30min，其分析结果见表15。
表15为对比例2制得的电容器的性能测试
序号 CAP(uF) DF(％) ESR(mΩ)/100kHz LC(uA)/1min
1 80.54 6.28 28.40 116.00
2 80.16 6.68 37.50 37.00
3 82.64 6.49 28.20 27.00
4 80.13 5.92 22.00 53.00
5 79.43 6.30 29.00 128.00
6 79.21 6.44 28.00 70.00
7 81.63 6.10 21.00 112.00
8 81.89 6.01 27.50 46.00
9 81.05 5.79 18.00 53.00
10 81.55 5.85 32.90 34.00
11 82.43 5.60 23.40 70.00
12 81.38 5.73 27.90 112.00
13 82.27 6.33 22.70 23.00
14 82.34 5.63 19.40 31.00
15 78.72 5.94 32.40 76.00
16 80.04 5.59 30.20 36.00
17 80.23 5.79 21.70 68.00
18 79.41 5.86 25.40 43.00
19 80.32 6.09 25.90 94.00
20 81.74 5.91 18.30 26.00
MIN 78.72 5.59 18.00 23.00
MAX 82.64 6.68 37.50 128.00
AVE 80.86 6.02 25.99 62.75
对比例3
该电容器的规格为16V 3300uF 18*36.5mm，其具体的制造方法为：
(1)阳极化成铝箔与阴极箔之间用电解纸一起卷绕成芯包；
(2)焊接在铁条上，浸入化成液中，使化成液刚好淹没芯包，施加32V的化成电压，同时对二个阳极化成铝箔进行化成修复处理，处理时间为10分钟；
(3)对芯包进行碳化处理，温度300±10℃，碳化时间20min；
(4)重复上述步骤(2)和(3)4次；
(5)将芯包分别放入单体中进行含浸，含浸时，使芯包的至少2/3处于含浸液面以下，含浸时间为6min，完毕后，去溶剂；
(6)将芯包放入氧化剂中进行含浸，含浸时，使芯包的全部处于含浸液面以下，含浸方法是先将内部为常压的芯包含浸于氧化剂中2min，再脱离氧化剂，抽真空至真空度90KPa以下，保持 2min，时间到后放气于常压，并通入压缩空气至压力为3atm，含浸于氧化剂中5min，时间到完成含浸；
(7)对含浸好的芯包进行两段式聚合：首先，低温聚合，聚合温度50±10℃，聚合时间200±10min；其次，高温聚合，聚合温度150±10℃，聚合时间100±10min；
(8)老化处理和测试分选：先向电容器的一极分别施以额定电压的0.5倍、1倍、1.2倍的电压进行老化处理，然后再向电容器的另一极分别施以额定电压的0.5倍、1倍、1.2倍的电压进行老化处理。
老化结束抽取20个进行测试，其CAP(uF)平均为3312；DF(％)平均为3.3；ESR(mΩ)/100kHz平均为6.3；LC(uA)/1min平均为153。
该对比例采用是单体与氧化剂采用的溶剂型溶剂，在含浸过程中，由于采用的溶剂表面张力小，能够渗透到化成箔的微孔中，在微孔中形成导电聚合物，微孔中的氧化膜缺陷较多，导电聚合物的存在，这些缺陷会产生较大的漏电流，并且导电聚合物的修复能力较差，故大漏电产生后，就可能出现短路，因此很难提高产品的电压。
对比例4
该电容器的制造方法中所用到的阳极箔、阴极箔及电解纸和规格与实施例5相同，作成电容器规格为200V100μF，尺寸Φ16*26mm，其具体的制造方法为：
(1)阳极化成铝箔与阴极箔之间用电解纸一起卷绕成芯包；
(2)将芯包置于300℃下进行碳化处理，除去灰份；再将芯包放在7％已二酸铵的水溶液中，施加9V电压进行15min修复损坏的氧化膜；
(3)将氧化剂对甲基苯磺酸铁配成40～60％的醇溶液，将步骤(2)处理后的芯包浸入上述醇溶液3～6min，取出芯包，置于60～70℃干燥除去醇溶液；
(4)将单体3,4乙烯二氧噻吩配成40～55％的醇溶液，将含浸氧化剂并烘干后的芯包含浸于单体的醇溶液中2～4min，取出芯包，置于60～70℃干燥除去醇溶液；升温至110～120℃使之产生聚合反应，形成导电高分子导电层；
(5)将芯包装上封口橡胶，放入铝壳中，施加电压老化100min，获得固体电解质铝电解电容器。
老化结束抽取20个进行测试，结果见表16。
表16为对比例4制得的电容器的性能测试
Figure PCTCN2015073533-appb-000021
Figure PCTCN2015073533-appb-000022
备注：由于对比例4中的方法耐压不足，不能测试进行老化处理，故漏电流没办法测试。
根据实施例和对比例，本发明采用常压、真空、加压多种压力环境结合的条件下将芯包浸入分散体A时，分散体A中的电解质能够更充分在箔的表面生成稳定的导电高分子层，提高电容器电性能；同时，聚合物分散体A作为固体电解质，能够有效提高高压固体电解质铝电解电容器的耐电压值；同时，采用多次重复含浸步骤，热处理后除去芯包中含浸溶剂，有利于下次对含浸液的吸收，可以获得更低ESR的高压固体电解质铝电解电容器，提高引出率，降低损耗同时可以提高产品的一致性；特别是(真空含浸+低温干燥)→(加压含浸+低温干燥)→(常压含浸+低温干燥+高温干燥)的循环含浸过程，更有利于下次对含浸液中导电聚合物的吸收，可以获得更低ESR，使芯包浸得更透更充分，获得稳定的导电高分子层。
制造电容器时采用真空状态含浸，其主要作用是将电解纸中、箔的表面以及箔微孔中的气体抽去，为分散体A的吸附腾出了空间，可以吸附更多的分散体A。若箔表面若有气泡，则会阻止分散体A的吸附，影响干燥后分散体A在箔表面形成膜的完整性，进而影响产品的性能。同时真空可以带走分散体A中的气泡，提高了分散体A的渗透效果。
而真空含浸后进入常压状态，主要是借助气体的压力，将浸在分散体A的芯包在一个大气压的条件下进一步的渗透，加压的原理是一样的，就是相对于真空有更大的压力差，使浸在分散体A中的芯包含浸得更加透彻，吸附更多的分散体A。
真空、常压和加压三种不同压力状态的结合可以在不同状态下有不同的压力，一步步加大压力，使芯包浸得更透更充分。
对于大尺寸如Φ16*26的电容器，由于芯包较大，分散体A经过的路径更长，更不宜渗透，单是真空和常压结合或者加压和常压结合很难实现芯包含浸效果，对其性能也造成一定的影响。
实施例11、实施例12与实施例13是在导电聚合物电解质中增加了导电能力更强的碳材料，来增加导电聚合物的导电性能。固体电解质的导电性能增强后，会直接降低产品的串联等效电阻(ESR)， 同时产品的损耗也会稍有降低。不同的加入方式会对产品有微小的差别，比如浓度，含浸的次序产品会有微小的差别，这些可能通过多次试验来完成优化。从实施例5中可以看出，因为没有碳材料增加导电性能，故没加导电碳材料的相比其串联等效电阻会增大，损耗也会有稍微的增加。
为了能够更好的实现固体电解质铝电解电容器的最佳性能，本发明还进行了工艺优化改进，以下结合正交优化实验进行说明。所述正交优化实验为7因素三水平，进行18次实验，老化结束后分别抽取20个进行测试，测试结果为其平均值，具体情况见表17。
表17为正交优化实验的因素及水平和性能测试
Figure PCTCN2015073533-appb-000023
这个正交试验不是完整意义上所有的条件的正交，只是选了7个影响因素比较大的做了个研究，实际生产工艺会由这个规律性的结果，与实际的生产以及生产效率结合起来，做一个性能与效率的综合，确定生产的工艺。
从这个正交试验来看：真空度不是越高越好，太低可能会导致芯包中的气体排不干净，会导致分散体A吸附不能完善；真空度太高，会造成分散体A中的水分散失，造成粘度增大，也会影响到实际的含浸效果。真空含浸时间在含浸中也有同产的问题，时间太短，含浸不充分，增长时间能够提高含浸效时，但超过一定的时间，提高的效果不明显，同时也会因时间太长，造成分散体A粘度大，造成下一个周期含浸不效果。
加压含浸的压力，对含浸效果在明显改善，加压含浸时间增长，含浸的效时也会改善。但可以实施的范围内，考虑到安全性，没有再增大压力。
低温干燥的目的，是让分散体中的水份慢慢排出芯包，温度过高至水沸腾的状态，会影响分散体在箔表面的聚合物膜的形成，温度过低会影响排出速度。时间增加会改善水份排出的效果，但时间太长不会明显增加效果并致使生产效率降低。高温干燥目的是进一步除去芯包中的水份，温度选择受高备的限制，高温干燥时间也要选择合适的时间，太长没有效果，同时会对产品作一些伤害。
因为目前分散体的固含量较低，选用多次含浸的方式，增加聚合物存有量，从试验结果来看， 增加到一定的次数后，性能提高效果就不明显。实验例中只时针对现在分散体的固含量进行的试验，固含量的变化，含浸次数会作变化。固含量越高，含浸次数可相应的减少。
以上对本发明实施例所提供的一种固体电解质铝电解电容器及其制造方法，进行了详细介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。

Claims (10)

  1. 一种固体电解质铝电解电容器，其特征在于，包括铝壳及设置在所述铝壳内的芯包，所述芯包包括阳极化成铝箔、阴极箔、介于所述阳极化成铝箔与阴极箔之间的电解纸和固体电解质，所述固体电解质包括导电聚合物和导电碳材料。
  2. 根据权利要求1所述的固体电解质铝电解电容器，其特征在于，所述导电聚合物为聚3,4乙烯二氧噻吩。
  3. 根据权利要求1所述的固体电解质铝电解电容器，其特征在于，所述导电碳材料为碳纳米材料或碳纳米复合材料。
  4. 一种固体电解质铝电解电容器的制造方法，包括：
    (1)将电容器的芯包焊于铁条上，施加电压进行化成，化成后进行清洗并干燥；
    (2)将干燥后的芯包浸入分散体B中，含浸时间1～30min；
    (3)将芯包移出分散体B，抽真空后再将芯包浸入分散体B，含浸时间1～10min；
    (4)将芯包保留在分散体B中，破真空，再加压，含浸时间1～10min；
    (5)将芯包保留在分散体B中，放气至常压，含浸时间1～10min；
    (6)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
    (7)步骤(3)至(6)至少重复一次；
    (8)入壳封口，老化处理获得固体电解质铝电解电容器；其中，
    所述分散体B为含导电聚合物和导电碳材料的分散体。
  5. 一种固体电解质铝电解电容器的制造方法，包括：
    (1)将电容器的芯包焊于铁条上，施加电压进行化成，化成后进行清洗并干燥；
    (2)将干燥后的芯包浸入分散体A中，含浸时间1～30min；
    (3)将芯包移出分散体A，抽真空后再将芯包浸入分散体A，含浸时间1～10min；
    (4)将芯包保留在分散体A中，破真空，再加压，含浸时间1～10min；
    (5)将芯包保留在分散体A中，放气至常压，含浸时间1～10min；
    (6)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
    (7)将干燥后的芯包浸入分散体C中，含浸时间1～30min；
    (8)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
    (9)步骤(3)至(8)至少重复一次；
    (10)入壳封口，老化处理获得固体电解质铝电解电容器；其中，
    所述分散体A和分散体C分别为含导电聚合物的分散体和含导电碳材料的分散体。
  6. 一种固体电解质铝电解电容器的制造方法，包括：
    (1)将电容器的芯包焊于铁条上，施加电压进行化成，化成后进行清洗并干燥；
    (2)将干燥后的芯包浸入分散体C中，含浸时间1～30min；
    (3)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
    (4)将干燥后的芯包浸入分散体A中，含浸时间1～30min；
    (5)将芯包移出分散体A，抽真空后再将芯包浸入分散体A，含浸时间1～10min；
    (6)将芯包保留在分散体A中，破真空，再加压，含浸时间1～10min；
    (7)将芯包保留在分散体A中，放气至常压，含浸时间1～10min；
    (8)取出芯包，将芯包置于65～100℃干燥20～60min，再将芯包置于135～165℃干燥20～60min；
    (9)步骤(5)至(8)至少重复一次；
    (10)入壳封口，老化处理获得固体电解质铝电解电容器；其中，
    所述分散体A和分散体C分别为含导电聚合物的分散体和含导电碳材料的分散体。
  7. 根据权利要求4至6任一所述的固体电解质铝电解电容器的制造方法，其特征在于，所述步骤(3)中抽真空的真空度为700～970Pa。
  8. 根据权利要求4至6任一所述的固体电解质铝电解电容器的制造方法，其特征在于，所述步骤(4)中加压为通入压缩空气，加压至0.1～0.6MPa。
  9. 根据权利要求4至6任一所述的固体电解质铝电解电容器的制造方法，其特征在于，所述导电碳材料为碳纳米材料或碳纳米复合材料；所述碳纳米材料为碳纳米管或石墨烯。
  10. 根据权利要求9所述的固体电解质铝电解电容器的制造方法，其特征在于，所述石墨烯粒径为小于200nm或碳纳米管长度为2～200nm。
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