Laminated aluminum electrolytic capacitor cathode material and preparation method and application thereof

Abstract

The invention relates to the technical field of capacitors, in particular to a laminated aluminum electrolytic capacitor cathode material and a preparation method and application thereof. The laminated aluminum electrolytic capacitor cathode material comprises a metal foil, and a coupling agent layer, a metal oxide layer and a conductive polymer layer which are sequentially formed on the metal foil. The laminated aluminum electrolytic capacitor prepared from the cathode material of the laminated aluminum electrolytic capacitor has smaller leakage current and longer service life.

Description

Technical Field

[0001] The present invention relates to the technical field of capacitors, and in particular to a cathode material for a laminated aluminum electrolytic capacitor, a preparation method, and an application thereof. Background Art

[0002] Multilayer aluminum electrolytic capacitors offer numerous advantages. Their low equivalent series resistance (ESR) reduces heat generation, improves power conversion efficiency, and stabilizes power output. Their high ripple current capability prevents overheating and performance degradation in applications like server power supplies. Their excellent high-frequency performance effectively filters noise in high-frequency circuits. Their long lifespan meets the demands of industrial equipment and other fields, while their high reliability enables stable operation in harsh environments. Their miniaturization facilitates the layout of portable electronic devices, while their diverse packaging options facilitate circuit design.

[0003] Currently, the leakage current of 6.3 V, 150 μF multilayer solid aluminum electrolytic capacitors is large and the life is short, which cannot meet the requirements of high performance guarantee of electronic components. Therefore, it is urgent to provide a multilayer aluminum electrolytic capacitor cathode material or a multilayer solid aluminum electrolytic capacitor to solve the above problems. Summary of the Invention

[0004] The present invention aims to at least partially address one of the technical problems in the related art. To this end, the present invention provides a cathode material for a laminated aluminum electrolytic capacitor, as well as a preparation method and application thereof. Laminated aluminum electrolytic capacitors made from this cathode material exhibit lower leakage current and longer lifespan.

[0005] To this end, the first aspect of the present invention provides a laminated aluminum electrolytic capacitor cathode material, comprising a metal foil and a coupling agent layer, a metal oxide layer, and a conductive polymer layer sequentially formed on the metal foil.

[0006] The provision of the coupling agent layer can enhance the adhesion between the metal oxide layer and the metal foil; the provision of the metal oxide layer can significantly reduce the leakage current of the laminated aluminum electrolytic capacitor; the conductive polymer is stable and not easily decomposed in water, oxygen and high temperature, thus making the laminated aluminum electrolytic capacitor have a longer life.

[0007] According to an embodiment of the present invention, the raw material for forming the coupling agent layer includes a coupling agent, and the coupling agent includes at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a chromium complex coupling agent, a metal composite coupling agent, a phosphate coupling agent, and a borate coupling agent.

[0008] According to an embodiment of the present invention, the metal oxide layer includes a manganese dioxide layer.

[0009] According to an embodiment of the present invention, the raw materials for forming the conductive polymer layer include polymer monomers, electrolytes, and surfactants.

[0010] According to an embodiment of the present invention, the molar ratio of the polymer monomer, the electrolyte and the surfactant is (0.2-0.6):(0.1-0.3):(0.1-0.3).

[0011] According to an embodiment of the present invention, the polymer monomer includes at least one of 3,4-ethylenedioxythiophene and pyrrole.

[0012] According to an embodiment of the present invention, the electrolyte includes tetraphenylporphyrin tetrasulfonic acid, tetraphenylporphyrin tetrasulfonate, polyphosphate, triphenylphosphine trisulfonate, tetrakis (4-sulfonatophenyl) methane, biphenyl-4-sulfonate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, naphthalenesulfonate, naphthalene disulfonate, naphthalene-1,3,6-trisulfonate, camphorsulfonate, sulfosalicylate, benzene disulfonate, butylnaphthalenesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, At least one of phthalate, phenol sulfonate, anthraquinone disulfonate, anthraquinone-2-sulfonate, methylene bisnaphthalene sulfonate, diisopropylnaphthalene sulfonate, phenylbenzimidazole sulfonate, tetrabutylammonium p-tolylsulfonate, nitrate, silicotungstate, phosphotungstate, polystyrene sulfonate, alginate, cyanurate, tripolyphosphate, alkyl diphenyl ether disulfonate, polydisulfide dipropane sulfonate, diphenyl sulfide sulfonate, sulfate, lignin sulfonate, and indigo disulfonate.

[0013] According to an embodiment of the present invention, the electrolyte is preferably at least one of sodium triphenylphosphine tris-metasulfonate, sodium tetraphenylporphyrin tetrasulfonate, sodium indigo disulfonate, sodium lignin sulfonate, and sodium polyphosphate.

[0014] According to an embodiment of the present invention, the surfactant includes at least one of dodecyl diphenyl ether disulfonate, bis-linear tetradecyl diphenylmethane disulfonate, dodecyl diphenyl ether disulfonate, dodecyl diphenyl sulfide sulfonate, dodecylbenzene sulfonate, dodecyl sulfonate, dodecyl alcohol polyoxyethylene ether sulfate, sodium dioctyl sulfosuccinate, N-oleoyl-N-methyl taurate, and lignin sulfonate.

[0015] According to an embodiment of the present invention, the surfactant is preferably at least one of sodium dodecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, sodium bis(linear tetradecyl diphenylmethane disulfonate), sodium dodecyl alcohol polyoxyethylene ether sulfate, and sodium dioctyl sulfosuccinate.

[0016] The second aspect of the present invention provides a method for preparing the cathode material of the laminated aluminum electrolytic capacitor described in the first aspect, comprising: The metal foil is separated into an anode area and a cathode area by using a barrier adhesive, and a coupling agent layer, a metal oxide layer and a conductive polymer layer are sequentially formed on the cathode area of ​​the metal foil. The cathode area in which the coupling agent layer, the metal oxide layer and the conductive polymer layer are sequentially formed is the cathode material of the laminated aluminum electrolytic capacitor.

[0017] The laminated aluminum electrolytic capacitor prepared based on the laminated aluminum electrolytic capacitor cathode material has smaller leakage current and longer service life.

[0018] According to an embodiment of the present invention, the step of forming the coupling agent layer includes: The cathode region of the metal foil is placed in a solution containing a coupling agent and subjected to a first immersion treatment to obtain the coupling agent layer.

[0019] According to an embodiment of the present invention, the mass fraction of the coupling agent in the solution containing the coupling agent is 1 wt %-5 wt %.

[0020] According to an embodiment of the present invention, the step of forming the metal oxide layer includes: The cathode region of the metal foil forming the coupling agent layer is placed in a solution containing a manganese salt and a thermal decomposition accelerator for a second immersion treatment, followed by dehydration and thermal decomposition treatment to obtain the metal oxide layer. The cathode region of the metal foil forming the coupling agent layer is placed in a solution containing a manganese salt and a thermal decomposition accelerator for a second immersion treatment, followed by dehydration and thermal decomposition treatment to obtain the metal oxide layer.

[0021] According to an embodiment of the present invention, the manganese salt includes at least one of manganese nitrate, potassium permanganate, and manganese carbonate.

[0022] According to an embodiment of the present invention, the thermal decomposition accelerator includes at least one of ethylene glycol amine, titanium dioxide, and ammonium citrate.

[0023] According to an embodiment of the present invention, the mass fraction of the manganese salt in the solution containing the manganese salt and the thermal decomposition accelerator is 50 wt%-70 wt%.

[0024] According to an embodiment of the present invention, the mass fraction of the thermal decomposition accelerator in the solution containing the manganese salt and the thermal decomposition accelerator is 2 wt%-8 wt%.

[0025] According to an embodiment of the present invention, the temperature of the second immersion treatment is 10°C-30°C.

[0026] According to an embodiment of the present invention, the duration of the second immersion treatment is 5 min-40 min.

[0027] According to an embodiment of the present invention, the temperature of the dehydration treatment is 100°C-180°C.

[0028] According to an embodiment of the present invention, the dehydration treatment time is 15 min-45 min.

[0029] According to an embodiment of the present invention, the temperature of the thermal decomposition treatment is 200°C-400°C.

[0030] According to an embodiment of the present invention, the thermal decomposition treatment time is 20 min-50 min.

[0031] According to an embodiment of the present invention, the step of forming the conductive polymer layer includes: The metal foil forming the metal oxide layer is used as an anode and placed in a solution containing a polymer monomer, an electrolyte and a surfactant to obtain the conductive polymer layer through electropolymerization.

[0032] According to an embodiment of the present invention, the concentration of the polymer monomer in the solution containing the polymer monomer, the electrolyte and the surfactant is 0.2 mol / L-0.6 mol / L.

[0033] According to an embodiment of the present invention, the concentration of the electrolyte in the solution containing the polymer monomer, the electrolyte and the surfactant is 0.1 mol / L-0.3 mol / L.

[0034] According to an embodiment of the present invention, the concentration of the surfactant in the solution containing the polymer monomer, the electrolyte and the surfactant is 0.1 mol / L-0.3 mol / L.

[0035] According to an embodiment of the present invention, the pH value of the solution containing the polymer monomer, electrolyte and surfactant is 2-6.

[0036] According to an embodiment of the present invention, the electropolymerization satisfies at least one of the following conditions: The temperature of the electropolymerization is 0°C-25°C; The scanning voltage cycle range was 0 V–1.6 V; Scan speed: 20 mV / s -70 mV / s; The number of scanning circles is 10-50 circles.

[0037] According to an embodiment of the present invention, the metal foil comprises a chemically formed foil.

[0038] A third aspect of the present invention provides an electrode foil comprising: an anode region and a cathode region, wherein the anode region and the cathode region are separated by a barrier adhesive to form a metal foil, and the cathode region is selected from the laminated aluminum electrolytic capacitor cathode material described in the first aspect or the laminated aluminum electrolytic capacitor cathode material prepared by the preparation method described in the second aspect.

[0039] The laminated aluminum electrolytic capacitor made based on the electrode foil has smaller leakage current and longer service life.

[0040] According to an embodiment of the present invention, the metal foil comprises a chemically formed foil.

[0041] According to an embodiment of the present invention, the anode region is not processed.

[0042] The fourth aspect of the present invention provides an application of the cathode material for a laminated aluminum electrolytic capacitor described in the first aspect, the cathode material for a laminated aluminum electrolytic capacitor prepared by the preparation method described in the second aspect, or the electrode foil described in the third aspect as an electrode material for a laminated aluminum electrolytic capacitor.

[0043] In a fifth aspect, the present invention provides a laminated aluminum electrolytic capacitor, wherein the cathode region of the laminated aluminum electrolytic capacitor comprises the laminated aluminum electrolytic capacitor cathode material described in the first aspect, or the laminated aluminum electrolytic capacitor cathode material obtained by the method described in the second aspect, or the electrode material of the laminated aluminum electrolytic capacitor comprises the electrode foil described in the third aspect.

[0044] Therefore, the multilayer aluminum electrolytic capacitor has a smaller leakage current and a longer life.

[0045] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0046] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be understood as limiting the present invention.

[0047] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be understood to indicate or imply relative importance or implicitly specify the number of the technical features indicated. Therefore, features defined as "first" or "second" may explicitly or implicitly include one or more of such features. Furthermore, in the description of the present invention, unless otherwise specified, "plurality" means two or more.

[0048] The term "wt%" means percent by weight.

[0049] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0050] In order to make the present invention more easily understood, certain technical and scientific terms are specifically defined below. Unless otherwise clearly defined elsewhere in this document, all other technical and scientific terms used herein have the meaning commonly understood by those skilled in the art to which the present invention belongs.

[0051] In this document, the terms “include” or “comprising” are open expressions, that is, including the contents specified in the present invention, but not excluding other contents.

[0052] As used herein, the terms "optionally," "optional," or "optionally" generally mean that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0053] According to an embodiment of the present invention, a first aspect of the present invention provides a laminated aluminum electrolytic capacitor cathode material, comprising a metal foil and a coupling agent layer, a metal oxide layer, and a conductive polymer layer sequentially formed on the metal foil.

[0054] According to a specific embodiment of the present invention, the raw materials for forming the coupling agent layer include a coupling agent. The type of the coupling agent is not particularly limited and can be selected by those skilled in the art according to the circumstances. As some specific examples, the coupling agent can include at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a chromium complex coupling agent, a metal composite coupling agent, a phosphate coupling agent, and a borate coupling agent, preferably a silane coupling agent such as KH171. Thus, the coupling agent layer can enhance the adhesion between the metal oxide layer and the metal foil.

[0055] According to a specific embodiment of the present invention, the metal oxide layer includes a manganese dioxide layer, thereby significantly reducing the leakage current of the stacked aluminum electrolytic capacitor.

[0056] According to a specific embodiment of the present invention, the raw materials for forming the conductive polymer layer include polymer monomers, electrolytes, and surfactants. The conductive polymer thus produced is more stable and less prone to decomposition in water, oxygen, and high temperatures, thereby extending the life of the laminated aluminum electrolytic capacitor.

[0057] Specifically, the molar ratio of the polymer monomer, the electrolyte, and the surfactant is (0.2-0.6):(0.1-0.3):(0.1-0.3). As some specific examples, the molar ratio of the polymer monomer, the electrolyte, and the surfactant may be 0.2:0.1:0.1, 0.2:0.1:0.3, 0.2:0.2:0.3, 0.2:0.3:0.3, 0.3:0.1:0.1, 0.3:0.2:0.2, 0.3:0.3:0.1, 0.4:0.1:0.1, 0.5:0.3:0.1, 0.6:0.1:0.1, 0.6:0.2:0.1, 0.6:0.2:0.2, 0.6:0.3:0.1, 0.6:0.3:0.3, and the like.

[0058] Specifically, the type of the polymer monomer is not particularly limited. As some specific examples, the polymer monomer may include at least one of 3,4-ethylenedioxythiophene and pyrrole.

[0059] Specifically, the type of the electrolyte is not particularly limited. As some specific examples, the electrolyte may include tetraphenylporphyrin tetrasulfonic acid, tetraphenylporphyrin tetrasulfonate, polyphosphate, triphenylphosphine trimesosulfonate, tetrakis(4-sulfonatophenyl)methane, biphenyl-4-sulfonate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, naphthalenesulfonate, naphthalene disulfonate, naphthalene-1,3,6-trisulfonate, camphorsulfonate, sulfosalicylate, benzene disulfonate, butylnaphthalenesulfonate, 9,10 At least one of dimethoxyanthracene-2-sulfonate, phenolsulfonate, anthraquinone disulfonate, anthraquinone-2-sulfonate, methylenebisnaphthalenesulfonate, diisopropylnaphthalenesulfonate, phenylbenzimidazolesulfonate, tetrabutylammonium p-tolylsulfonate, nitrate, silicotungstate, phosphotungstate, polystyrenesulfonate, alginate, cyanurate, tripolyphosphate, alkyl diphenyl ether disulfonate, polydipropylene disulfide sulfonate, diphenyl sulfide sulfonate, sulfate, ligninsulfonate, and indigo disulfonate. The use of a larger, more negatively charged electrolyte makes the resulting conductive polymer more stable and less prone to decomposition in water, oxygen, and high temperatures, thereby extending the life of the laminated aluminum electrolytic capacitor.

[0060] More specifically, various salt electrolytes such as sodium salt can be used.

[0061] According to a specific embodiment of the present invention, the type of the surfactant is not particularly limited. As some specific examples, the surfactant may include at least one of dodecyl diphenyl ether disulfonate, bis-linear tetradecyl diphenylmethane disulfonate, dodecyl diphenyl ether disulfonate, dodecyl diphenyl sulfide sulfonate, dodecylbenzene sulfonate, dodecyl sulfonate, dodecyl alcohol polyoxyethylene ether sulfate, sodium dioctyl sulfosuccinate, N-oleoyl-N-methyl taurate, and lignin sulfonate.

[0062] More specifically, various salt-based surfactants may be sodium salts or the like.

[0063] According to an embodiment of the present invention, a second aspect of the present invention provides a method for preparing the cathode material of the laminated aluminum electrolytic capacitor according to the first aspect, comprising: The metal foil is separated into an anode area and a cathode area by using a barrier adhesive, and a coupling agent layer, a metal oxide layer and a conductive polymer layer are sequentially formed on the cathode area of ​​the metal foil. The cathode area in which the coupling agent layer, the metal oxide layer and the conductive polymer layer are sequentially formed is the cathode material of the laminated aluminum electrolytic capacitor.

[0064] According to a specific embodiment of the present invention, the type of metal foil is not particularly limited and can be a commonly used metal foil type in the art, such as chemically formed foil. Furthermore, the chemically formed foil can be subjected to pre-treatments such as cleaning, gluing, and chemically forming. Specifically, the cleaning can be performed using conventional cleaning processes in the art. The gluing process forms a separation area between the anode and cathode regions on the metal foil, and the chemically formed foil is obtained through chemically forming. The coupling agent layer, metal oxide layer, and conductive polymer layer are then prepared on the cathode region of the chemically formed foil.

[0065] According to a specific embodiment of the present invention, the step of forming the coupling agent layer includes: The cathode region of the metal foil is placed in a solution containing a coupling agent and subjected to a first immersion treatment to obtain the coupling agent layer.

[0066] Specifically, the mass fraction of the coupling agent in the solution containing the coupling agent is 1 wt%-5 wt%, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt% or any value in the range between any two of these values. The coupling agent is selected as described above.

[0067] Specifically, the temperature of the first immersion treatment is not particularly limited. As some specific examples, the temperature of the first immersion treatment is 15-35°C, such as 15°C, 20°C, 25°C, 30°C, 35°C, or any value in the range between any two values.

[0068] Specifically, the time of the first immersion treatment is not particularly limited. As some specific examples, the time of the first immersion treatment is 5-10 min, such as 5 min, 6 min, 7 min, 8 min, 9 min, 10 min or any value in the range between any two values.

[0069] Specifically, after the first impregnation treatment, a drying treatment may be performed to obtain the coupling agent layer. The temperature and time of the drying treatment are not particularly limited, as long as a drying effect is achieved. As some specific examples, the drying treatment temperature may be 80-120°C (e.g., 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, or any value in a range between any two of these values), and the drying time may be 8-15 minutes (e.g., 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, or any value in a range between any two of these values).

[0070] According to a specific embodiment of the present invention, the step of forming the metal oxide layer includes: The cathode area of ​​the metal foil forming the coupling agent layer is placed in a solution containing a manganese salt and a thermal decomposition accelerator for a second immersion treatment, and the metal oxide layer is obtained through dehydration treatment and thermal decomposition treatment.

[0071] Specifically, the type of manganese salt is not particularly limited and can be selected by those skilled in the art according to circumstances. As some specific examples, the manganese salt can include at least one of manganese nitrate, potassium permanganate, and manganese carbonate. The manganese dioxide formed by thermal decomposition is thus more dense, significantly reducing the leakage current of the laminated aluminum electrolytic capacitor.

[0072] Specifically, the type of thermal decomposition accelerator is not particularly limited and can be selected by those skilled in the art according to circumstances. As some specific examples, the thermal decomposition accelerator includes at least one of ethylene glycolamine, titanium dioxide, and ammonium citrate. This provides active sites or alters the reaction pathway, thereby reducing the activation energy of the reaction and causing the manganese salt to decompose at a lower temperature.

[0073] Specifically, the mass fraction of the manganese salt in the solution containing the manganese salt and the thermal decomposition promoter is not particularly limited, and those skilled in the art can select it according to the circumstances. As some specific examples, the mass fraction of the manganese salt in the solution containing the manganese salt and the thermal decomposition promoter is 50 wt%-70 wt%, for example, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt% or any value in the range between any two of these values.

[0074] Specifically, the mass fraction of the thermal decomposition promoter in the solution containing the manganese salt and the thermal decomposition promoter is not particularly limited, and those skilled in the art can select it according to the circumstances. As some specific examples, the mass fraction of the thermal decomposition promoter in the solution containing the manganese salt and the thermal decomposition promoter is 2 wt%-8 wt%, for example, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6wt%, 7 wt%, 8 wt% or any value in the range between any two of these values.

[0075] Specifically, the temperature and time of the second immersion treatment are not particularly limited, and those skilled in the art can select them according to the circumstances. As some specific examples, the temperature of the second immersion treatment is 10-30°C, for example, 10°C, 15°C, 20°C, 25°C, 30°C, or any value in the range between any two values ​​therein; the time of the second immersion treatment is 5-40min, for example, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, or any value in the range between any two values ​​therein.

[0076] Specifically, the temperature and time of the dehydration treatment are not particularly limited, and those skilled in the art can select them according to the circumstances. As some specific examples, the temperature of the dehydration treatment is 100-180°C, for example, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C or any value in the range between any two of them; the time of the dehydration treatment is 15-45 min, for example, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min or any value in the range between any two of them.

[0077] Specifically, the temperature and time of the thermal decomposition treatment are not particularly limited, and those skilled in the art can select them according to the circumstances. As some specific examples, the temperature of the thermal decomposition treatment is 200-400°C, for example, 200°C, 250°C, 300°C, 400°C, or any value in the range between any two values ​​thereof; the time of the thermal decomposition treatment is 20-50min, for example, 20 min, 30 min, 40 min, 50 min, or any value in the range between any two values ​​thereof.

[0078] According to a specific embodiment of the present invention, the method further comprises the following steps of preparing the conductive polymer layer: The metal foil forming the metal oxide layer is used as an anode and placed in a solution containing a polymer monomer, an electrolyte and a surfactant to obtain the conductive polymer layer through electropolymerization.

[0079] Specifically, the polymer monomer, electrolyte and surfactant are as described above.

[0080] Specifically, the concentration of the polymer monomer in the solution containing the polymer monomer, the electrolyte and the surfactant is not particularly limited, and those skilled in the art can select it according to the circumstances. As some specific examples, the concentration of the polymer monomer in the solution containing the polymer monomer, the electrolyte and the surfactant can be 0.2 mol / L-0.6 mol / L, for example, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L or any value in the range between any two values.

[0081] Specifically, the concentration of the electrolyte in the solution containing the polymer monomer, the electrolyte and the surfactant is not particularly limited, and those skilled in the art can select it according to the circumstances. As some specific examples, the concentration of the electrolyte in the solution containing the polymer monomer, the electrolyte and the surfactant can be 0.1-0.3 mol / L, for example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L or any value in the range between any two values.

[0082] Specifically, the concentration of the surfactant in the solution containing the polymer monomer, the electrolyte and the surfactant is not particularly limited, and those skilled in the art can select it according to the circumstances. As some specific examples, the concentration of the surfactant in the solution containing the polymer monomer, the electrolyte and the surfactant is 0.1 mol / L-0.3 mol / L, for example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L or any value in the range between any two of these values.

[0083] Specifically, the pH value of the solution containing the polymer monomer, electrolyte, and surfactant is 2-6. As some specific examples, the pH value of the solution containing the polymer monomer, electrolyte, and surfactant may be 2, 3, 4, 5, 6, etc. The target pH value may be achieved by adding a pH adjuster to the solution containing the polymer monomer, electrolyte, and surfactant. The pH adjuster may include at least one of biphenyl-4-sulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, camphorsulfonic acid, and sulfuric acid.

[0084] Specifically, the electropolymerization is performed by placing the metal foil forming the metal oxide layer and the external electrode as anodes, a counter electrode, and a reference electrode in a solution containing polymer monomers, an electrolyte, and a surfactant to perform electropolymerization.

[0085] More specifically, the counter electrode may be selected from one of a platinum electrode, a carbon electrode, a silver electrode, a stainless steel electrode, and an ITO conductive glass electrode. The reference electrode may be selected from one of a saturated calomel electrode, a silver / silver chloride electrode, a standard hydrogen electrode, a copper / copper sulfate electrode, a platinum electrode, a mercury / mercuric oxide electrode, and a mercury / mercurous sulfate electrode.

[0086] Specifically, the temperature of the electropolymerization is not particularly limited and can be selected by those skilled in the art according to circumstances. As some specific examples, the temperature of the electropolymerization can be 0-25°C, such as 0°C, 5°C, 10°C, 15°C, 20°C, 25°C or any value in the range between any two of these values.

[0087] Specifically, the electropolymerization setting scanning potential cycle range is 0-1.6 V. As some specific examples, the scanning potential cycle range can be 0-1.3 V, 0-1.4 V, 0-1.5 V, 0-1.6 V, etc.

[0088] Specifically, the electropolymerization scan speed is set to 20-70 mV / s. As some specific examples, the electropolymerization scan speed is set to 20 mV / s, 30 mV / s, 40 mV / s, 50 mV / s, 60 mV / s, 70 mV / s or any value in the range between any two values.

[0089] Specifically, the number of scanning circles set by electropolymerization is 10-50 circles. As some specific examples, the number of scanning circles set by electropolymerization is 10 circles, 20 circles, 30 circles, 40 circles, 50 circles or any value in the range between any two values.

[0090] Specifically, after electropolymerization, a cleaning treatment may be performed, and the cleaning agent may include pure water, etc. The cleaning temperature and time may be selected according to the situation. For example, the cleaning temperature is 15°C-30°C (for example, 15°C, 20°C, 25°C, 30°C or any value in the range between any two values), and the time is 2 min-10 min (for example, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8, 9 min, 10 min or any value in the range between any two values).

[0091] According to an embodiment of the present invention, a third aspect of the present invention provides an electrode foil, comprising: an anode region and a cathode region, wherein the anode region and the cathode region are separated by a barrier glue to form a metal foil, and the cathode region is selected from the laminated aluminum electrolytic capacitor cathode material described in the first aspect or the laminated aluminum electrolytic capacitor cathode material prepared by the preparation method described in the second aspect.

[0092] According to a specific embodiment of the present invention, the type of the metal foil is not particularly limited, and a commonly used metal foil type in the art, such as chemically formed foil, may be used.

[0093] According to a specific embodiment of the present invention, the anode region is not treated.

[0094] According to an embodiment of the present invention, the fourth aspect of the present invention provides an application of the cathode material of the laminated aluminum electrolytic capacitor described in the first aspect, the cathode material of the laminated aluminum electrolytic capacitor prepared by the preparation method described in the second aspect, or the electrode foil described in the third aspect as an electrode material for a laminated aluminum electrolytic capacitor.

[0095] According to an embodiment of the present invention, a fifth aspect of the present invention provides a laminated aluminum electrolytic capacitor, wherein the cathode region of the laminated aluminum electrolytic capacitor comprises the laminated aluminum electrolytic capacitor cathode material described in the first aspect, or the laminated aluminum electrolytic capacitor cathode material obtained using the method described in the second aspect, or the electrode material of the laminated aluminum electrolytic capacitor comprises the electrode foil described in the third aspect. Thus, the laminated aluminum electrolytic capacitor has low leakage current and a long service life.

[0096] According to a specific embodiment of the present invention, the preparation of the cathode area also includes a lead-out layer, which is arranged on the surface of the conductive polymer layer away from the metal oxide layer. The lead-out layer can be obtained by conventional methods in the art, for example, the cathode area of ​​the chemically formed foil forming the conductive polymer layer is immersed in graphite slurry, dried, and then immersed in silver paste, and dried to obtain the cathode area.

[0097] According to a specific embodiment of the present invention, the laminated aluminum electrolytic capacitor includes a battery core, the battery core includes a monolithic capacitor, the monolithic capacitor includes an anode region, a cathode region and an isolation region, the isolation region is arranged between the anode region and the cathode region, and the cathode region includes the laminated aluminum electrolytic capacitor cathode material described in the first aspect, or the laminated aluminum electrolytic capacitor cathode material obtained by the method described in the second aspect.

[0098] Specifically, the number of the monolithic capacitors is not particularly limited, and those skilled in the art can adjust it according to circumstances. For example, the number of the monolithic capacitors is one or more. When there are multiple monolithic capacitors, they can be stacked to form a battery core.

[0099] Specifically, the anode regions of the prepared monolithic capacitors can be stacked and connected by welding, while the cathode regions can be stacked and connected by conductive silver glue. After curing, the cells are obtained. The cells are then packaged and formed to form a laminated aluminum electrolytic capacitor, which can then be aged and subjected to other treatments.

[0100] The present invention will be explained below with reference to the examples. Those skilled in the art will appreciate that the following examples are intended to illustrate the present invention only and should not be construed as limiting the scope of the invention. Where specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature in this field or in the product specifications are used. Reagents or instruments used without manufacturer specified are commercially available conventional products. The chemically formed foils employed are prepared by conventional methods or are commercially available conventional chemically formed foils.

[0101] Polyimide glue: Manufacturer: Shenzhen Jipeng Silicone Fluorine Materials Co., Ltd.

[0102] Silane coupling agent KH171: vinyltrimethoxysilane, i.e. CH2=CHSi(OCH3)3.

[0103] Example 1 (1) Pretreatment of chemical foil: A 13 V electrolytic foil was punched into 6 mm × 3.5 mm dimensions. A polyimide adhesive barrier was applied to the cut foil to divide it into anode and cathode regions. The cathode region was 5 mm high and 0.25 mm wide. The foil was then cured at 150°C for 25 minutes. The cathode region of the electrolytic foil was then cross-sectioned and repaired. The electrolyte was a 10% ammonium adipate aqueous solution at 80°C. The applied voltage was 13 V and maintained for 10 minutes.

[0104] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0105] Manganese nitrate was prepared into a 60% by mass aqueous solution, and 4 wt% of ethylene glycolamine was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated at 130°C for 20 minutes and then thermally decomposed at 230°C for 30 minutes. This process was repeated twice.

[0106] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 15°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium triphenylphosphine tris-metasulfonate, and 0.1 mol / L sodium dodecyldiphenyl ether disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. The cyclic voltammetry parameters were: scan voltage range 0-1.5 V, scan rate 50 mV / s, and number of scans 25 times. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0107] (3) Preparation of lead layer: The cathode area of ​​the electrochemical foil coated with a conductive polymer was immersed in a graphite slurry with a solid content of 5 wt% and a viscosity of 10 CP for 10 s, then slowly pulled out, naturally dried for 5 min, and then dried at 120 °C for 20 min to solidify; then the electrochemical foil was immersed in a silver paste with a solid content of 15 wt% and a viscosity of 120 CP for 10 s, then slowly pulled out, naturally dried for 5 min, and then dried at 150 °C for 30 min to solidify.

[0108] (4) Preparation of battery cells: The anode sections of the prepared monolithic capacitors were stacked and soldered to a lead frame, while the cathode sections were stacked and connected using conductive silver glue. The resulting cells were heat-cured under pressure at 150°C for 30 minutes to create a compact cell.

[0109] (5) Cell packaging and molding: The cells are encapsulated with epoxy resin, and the lead frame of the welded cells is placed in a plastic encapsulation mold. The mold is then closed, preheated, and plasticized epoxy resin is injected. The mold is then held under pressure, cooled, opened, and ejected to create the encapsulated product. The encapsulated capacitor is then passed through a rib cutting and molding machine to remove the lead frame, followed by leg bending and molding, resulting in a complete laminated solid aluminum electrolytic capacitor.

[0110] (6) Capacitor aging: The capacitors were aged, first at room temperature and then at high temperature. The voltage was first increased to 1.25 times the enabling voltage at room temperature at a rate of 0.2 V / min. After increasing to 0.7 times the enabling voltage, the capacitors were aged at room temperature for 90 minutes, followed by high-temperature aging at 125°C for 180 minutes. The final capacitor dimensions were 7.3 mm × 4.33 mm × 1.9 mm.

[0111] Example 2 (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0112] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0113] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% ethylene glycolamine was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 120°C for 30 minutes and then programmed to 250°C for thermal decomposition for 20 minutes. This process was repeated twice.

[0114] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2 Cyclic voltammetry electropolymerization was performed at 15°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium tetraphenylporphyrin tetrasulfonate, and 0.1 mol / L sodium dodecyldiphenyl oxide disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Prior to polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. Cyclic voltammetry parameters were set as follows: scan voltage range 0-1.5 V, scan rate 50 mV / s, and scan number 25. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0115] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0116] (4) The preparation of the battery cell is the same as in Example 1.

[0117] (5) The cell packaging and molding are the same as in Example 1.

[0118] (6) Capacitor aging is the same as in Example 1.

[0119] Example 3 (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0120] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0121] Manganese nitrate was prepared into a 60% aqueous solution, and 4 wt% ethylene glycolamine was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 130°C for 20 minutes and then programmed to 230°C for thermal decomposition for 30 minutes. This process was repeated twice.

[0122] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2 Cyclic voltammetry electropolymerization was performed at 5°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium indigo disulfonate, and 0.1 mol / L sodium bis(tetradecyldiphenylmethane)disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. The cyclic voltammetry parameters were: scan voltage range 0-1.5 V, scan rate 50 mV / s, and scan number 30. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0123] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0124] (4) The preparation of the battery cell is the same as in Example 1.

[0125] (5) The cell packaging and molding are the same as in Example 1.

[0126] (6) Capacitor aging is the same as in Example 1.

[0127] Example 4 (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0128] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0129] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% ethylene glycolamine was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 130°C for 30 minutes and then programmed to 250°C for thermal decomposition for 40 minutes. This process was repeated twice.

[0130] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2 Cyclic voltammetry electropolymerization was performed at 0°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium lignin sulfonate, and 0.1 mol / L sodium dodecyl alcohol polyoxyethylene ether sulfate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. The cyclic voltammetry parameters were: scan voltage range 0-1.5 V, scan rate 50 mV / s, and number of scans 40 times. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0131] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0132] (4) The preparation of the battery cell is the same as in Example 1.

[0133] (5) The cell packaging and molding are the same as in Example 1.

[0134] (6) Capacitor aging is the same as in Example 1.

[0135] Example 5 (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0136] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0137] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% ethylene glycolamine was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 130°C for 30 minutes and then programmed to 250°C for thermal decomposition for 40 minutes. This process was repeated twice.

[0138] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 0°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium polyphosphate, and 0.1 mol / L sodium dioctyl sulfosuccinate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. Cyclic voltammetry parameters were set as follows: scan voltage range 0-1.5 V, scan rate 50 mV / s, and scan number 40. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0139] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0140] (4) The preparation of the battery cell is the same as in Example 1.

[0141] (5) The cell packaging and molding are the same as in Example 1.

[0142] (6) Capacitor aging is the same as in Example 1.

[0143] Comparative Example 1: Electrolyte Investigation (1) The pre-treatment of the formed foil was the same as in Example 1.

[0144] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0145] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% ethylene glycolamine was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 120°C for 30 minutes and then programmed to 250°C for thermal decomposition for 20 minutes. This process was repeated twice.

[0146] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 15°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium dodecylsulfonate, and 0.1 mol / L sodium dodecyldiphenyl ether disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. The cyclic voltammetry parameters were: scan voltage range 0-1.5 V, scan rate 50 mV / s, and number of scans 25 times. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0147] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0148] (4) The preparation of the battery cell is the same as in Example 1.

[0149] (5) The cell packaging and molding are the same as in Example 1.

[0150] (6) Capacitor aging is the same as in Example 1.

[0151] Comparative Example 2: Electrolyte Investigation (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0152] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0153] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% ethylene glycolamine was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 120°C for 30 minutes and then programmed to 250°C for thermal decomposition for 20 minutes. This process was repeated twice.

[0154] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 15°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium persulfate, and 0.1 mol / L sodium dodecyldiphenyl ether disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. The cyclic voltammetry parameters were: scan voltage range 0-1.5 V, scan rate 50 mV / s, and scan number 25. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0155] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0156] (4) The preparation of the battery cell is the same as in Example 1.

[0157] (5) The cell packaging and molding are the same as in Example 1.

[0158] (6) Capacitor aging is the same as in Example 1.

[0159] Comparative Example 3: Electrolyte Investigation (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0160] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0161] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% ethylene glycolamine was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 120°C for 30 minutes and then programmed to 250°C for thermal decomposition for 20 minutes. This process was repeated twice.

[0162] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 15°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium p-toluenesulfonate, and 0.1 mol / L sodium dodecyldiphenyl ether disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. Cyclic voltammetry parameters were set as follows: scan voltage range 0-1.5 V, scan rate 50 mV / s, and number of scans 25 times. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0163] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0164] (4) The preparation of the battery cell is the same as in Example 1.

[0165] (5) The cell packaging and molding are the same as in Example 1.

[0166] (6) Capacitor aging is the same as in Example 1.

[0167] Comparative Example 4: Investigation of Thermal Decomposition Accelerator (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0168] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0169] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% titanium dioxide was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 120°C for 30 minutes, and then programmed to 250°C for thermal decomposition for 20 minutes. This process was repeated twice.

[0170] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 0°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium triphenylphosphine tris-metasulfonate, and 0.1 mol / L sodium dodecyldiphenyl ether disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. The cyclic voltammetry parameters were: scan voltage range 0-1.5 V, scan rate 50 mV / s, and number of scans 40 times. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0171] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0172] (4) The preparation of the battery cell is the same as in Example 1.

[0173] (5) The cell packaging and molding are the same as in Example 1.

[0174] (6) Capacitor aging is the same as in Example 1.

[0175] Comparative Example 5: Investigation of Thermal Decomposition Accelerator (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0176] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0177] Manganese nitrate was prepared into a 60% by mass aqueous solution, and 4 wt% urea was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 120°C for 30 minutes, and then programmed to 250°C for thermal decomposition for 20 minutes. This process was repeated twice.

[0178] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 0°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium tetraphenylporphyrin tetrasulfonate, and 0.1 mol / L sodium dodecyldiphenyl ether disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. Cyclic voltammetry parameters were set as follows: scan voltage range 0-1.5 V, scan rate 50 mV / s, and number of scans 40 times. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0179] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0180] (4) The preparation of the battery cell is the same as in Example 1.

[0181] (5) The cell packaging and molding are the same as in Example 1.

[0182] (6) Capacitor aging is the same as in Example 1.

[0183] Comparative Example 6: Investigation of Thermal Decomposition Accelerator (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0184] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0185] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% polyvinylpyrrolidone was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 120°C for 30 minutes, and then programmed to 250°C for thermal decomposition for 20 minutes. This process was repeated twice.

[0186] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 0°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium indigo disulfonate, and 0.1 mol / L sodium dodecyldiphenyl ether disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. The cyclic voltammetry parameters were: scan voltage range 0-1.5 V, scan rate 50 mV / s, and number of scans 40 times. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0187] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0188] (4) The preparation of the battery cell is the same as in Example 1.

[0189] (5) The cell packaging and molding are the same as in Example 1.

[0190] (6) Capacitor aging is the same as in Example 1.

[0191] Comparative Example 7: Investigation of Thermal Decomposition Accelerator (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0192] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0193] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% ammonium citrate was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 120°C for 30 minutes, and then programmed to 250°C for thermal decomposition for 20 minutes. This process was repeated twice.

[0194] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 0°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium lignin sulfonate, and 0.1 mol / L sodium dodecyldiphenyl ether disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Prior to polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. Cyclic voltammetry parameters were set as follows: scan voltage range 0-1.5 V, scan rate 50 mV / s, and scan number 40. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0195] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0196] (4) The preparation of the battery cell is the same as in Example 1.

[0197] (5) The cell packaging and molding are the same as in Example 1.

[0198] (6) Capacitor aging is the same as in Example 1.

[0199] Comparative Example 8: Investigation of Thermal Decomposition Accelerator (1) The pretreatment of the chemically formed foil is the same as that in Example 1.

[0200] (2) Preparation of cathode region: The cathode area of ​​the chemically repaired foil was immersed in a 3% by mass silane coupling agent KH171 aqueous solution for surface treatment, then naturally dried for 20 min and finally dried at 120 °C for 15 min.

[0201] Manganese nitrate was prepared as a 60% aqueous solution, and 4 wt% ammonium oxalate was added as a thermal decomposition accelerator to obtain a manganese nitrate aqueous solution containing a thermal decomposition accelerator. The cathode area of ​​the metal foil forming the coupling agent layer was immersed in the manganese nitrate aqueous solution containing a thermal decomposition accelerator at 20°C for 10 minutes. The solution was then dehydrated in a muffle furnace at 120°C for 30 minutes, and then programmed to 250°C for thermal decomposition for 20 minutes. This process was repeated twice.

[0202] The cathode area of ​​the electroless foil where manganese dioxide was deposited was connected to an external electrode as an anode with a spacing of 2 cm. 2Cyclic voltammetry electropolymerization was performed at 0°C in an electrolyte containing 0.4 mol / L 3,4-ethylenedioxythiophene, 0.3 mol / L sodium polyphosphate, and 0.1 mol / L sodium dodecyldiphenyl ether disulfonate using a calomel electrode as the cathode and a platinum electrode as the reference electrode. The pH of the electrolyte was controlled at 4 by the addition of biphenyl-4-sulfonic acid. Before polymerization, the electrolyte was deoxygenated with nitrogen for 10 minutes. The cyclic voltammetry parameters were: scan voltage range 0-1.5 V, scan rate 50 mV / s, and number of scans 40 times. After polymerization, the foil was rinsed with pure water for 5 minutes.

[0203] (3) The lead-out layer is prepared in the same manner as in Example 1.

[0204] (4) The preparation of the battery cell is the same as in Example 1.

[0205] (5) The cell packaging and molding are the same as in Example 1.

[0206] (6) Capacitor aging is the same as in Example 1.

[0207] Test Case The following tests were performed on the laminated aluminum electrolytic capacitors obtained in each embodiment and comparative example: (1) Capacity test Principle: An AC signal (usually 1 kHz to 1 MHz) is applied to the capacitor, the impedance (Z) is measured, and the capacitance value is calculated using the formula C = 1 / 2πfZ.

[0208] step: 1. Set the test frequency of the LCR meter (usually 1 kHz).

[0209] 2. Select the test mode as "C" (capacitance).

[0210] 3. Connect the capacitor and ensure the polarity is correct (electrolytic capacitors must distinguish between positive and negative poles).

[0211] 4. Read the capacitance value and additional parameters (such as ESR, dissipation factor).

[0212] (2) Operating voltage Multimeter method: measure the rated voltage or working voltage (DC) of the capacitor.

[0213] step: 1. Discharge capacitor: Use a wire to short-circuit the two poles of the capacitor to release the residual charge.

[0214] 2. Select the gear: Set the multimeter to the DC voltage gear (the range must be higher than the rated voltage of the capacitor).

[0215] 3. Connect the capacitor: Connect the red test lead to the positive terminal of the capacitor (the polarity of the electrolytic capacitor must be distinguished), and the black test lead to the negative terminal.

[0216] 4. Read the value: Measure the voltage across the capacitor.

[0217] (3) Leakage current Leakage current test method: Use the direct detection method to directly obtain the leakage current value by measuring the current between the equipment casing and the ground wire.

[0218] Steps: 1. Connect a microampere ammeter to the ground connection of the device housing. Observe the ammeter reading. If there are large fluctuations, check for environmental noise interference.

[0219] Leakage current test pass standard: I ≦ 0.1CV (μA) [test voltage 6.3V / 2min, capacitor capacity C / 150μF, if the measured leakage current exceeds 94.5μA, it is unqualified].

[0220] 2. Steps 2.1 Setting stress conditions: Temperature: 125℃; Voltage: operating voltage; Frequency: 100kHz.

[0221] 2.2 Continuous pressurization: Examples 1-5 maintained the stress conditions for 3500 h (test end time point), and Comparative Examples 1-8 maintained the stress conditions for 1500 h (test end time point).

[0222] 2.3 Record data: monitor leakage current value.

[0223] The test results are shown in Table 1.

[0224] Table 1

[0225] in conclusion: (1) As can be seen from Table 1, the capacity of the laminated aluminum electrolytic capacitors prepared in the Examples and Comparative Examples is distributed within a certain range. Affected by process stability, the reasonable actual capacity is generally 80%-120% of the design capacity. In addition, because the Comparative Example uses a thermal decomposition promoter not specified in the present invention when preparing the metal oxide layer, the thermal decomposition temperature of the manganese salt is relatively high. At the same time, because the Comparative Example uses an electrolyte with a smaller molecular volume and less negative charge, such as sodium persulfate, the resulting conductive polymer has poor thermal stability, thereby reducing the service life of the laminated aluminum electrolytic capacitor.

[0226] (2) Compared with other thermal decomposition accelerators (such as titanium dioxide, urea, polyvinyl pyrrolidone, ammonium citrate, ammonium oxalate, etc.), the present invention preferably uses ethylene glycol amine as the thermal decomposition accelerator, which is more conducive to reducing the leakage current of the obtained product and improving the safety, and has unexpected excellent technical effects.

[0227] (3) Compared with other electrolytes (such as sodium dodecylsulfonate, sodium persulfate, and sodium p-toluenesulfonate), the electrolyte provided by the present invention (such as sodium triphenylphosphine tris-metasulfonate, sodium tetraphenylporphyrin tetrasulfonate, sodium indigo disulfonate, sodium ligninsulfonate and / or sodium polysulfonate) is more conducive to reducing the leakage current of the obtained product and improving the safety, and has unexpected excellent technical effects.

[0228] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0229] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A cathode material for a laminated aluminum electrolytic capacitor, characterized in that: The invention comprises a metal foil and a coupling agent layer, a metal oxide layer and a conductive polymer layer sequentially formed on the metal foil.

2. The cathode material for a laminated aluminum electrolytic capacitor according to claim 1, wherein: The raw material for forming the coupling agent layer includes a coupling agent, and the coupling agent includes at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a chromium complex coupling agent, a metal composite coupling agent, a phosphate coupling agent, and a borate coupling agent; Optionally, the metal oxide layer comprises a manganese dioxide layer.

3. The cathode material for a laminated aluminum electrolytic capacitor according to any one of claims 1 to 2, characterized in that: The raw materials for forming the conductive polymer layer include polymer monomers, electrolytes and surfactants; Optionally, the molar ratio of the polymer monomer, electrolyte and surfactant is (0.2-0.6):(0.1-0.3):(0.1-0.3).

4. The cathode material for laminated aluminum electrolytic capacitors according to claim 3, wherein: The polymer monomer includes at least one of 3,4-ethylenedioxythiophene and pyrrole; Optionally, the electrolyte includes tetraphenylporphyrin tetrasulfonic acid, tetraphenylporphyrin tetrasulfonate, polyphosphate, triphenylphosphine trimesosulfonate, tetrakis(4-sulfonatophenyl)methane, biphenyl-4-sulfonate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, naphthalenesulfonate, naphthalene disulfonate, naphthalene-1,3,6-trisulfonate, camphorsulfonate, sulfosalicylate, benzene disulfonate, butylnaphthalenesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, At least one of phenol sulfonate, anthraquinone disulfonate, anthraquinone-2-sulfonate, methylene bisnaphthalene sulfonate, diisopropylnaphthalene sulfonate, phenylbenzimidazole sulfonate, tetrabutylammonium p-toluenesulfonate, nitrate, silicotungstate, phosphotungstate, polystyrene sulfonate, alginate, cyanurate, tripolyphosphate, alkyl diphenyl ether disulfonate, polydisulfide dipropane sulfonate, diphenyl sulfide sulfonate, sulfate, lignin sulfonate, and indigo disulfonate; Optionally, the surfactant includes at least one of dodecyl diphenyl ether disulfonate, bis-linear tetradecyl diphenylmethane disulfonate, dodecyl diphenyl ether disulfonate, dodecyl diphenyl sulfide sulfonate, dodecylbenzene sulfonate, dodecyl sulfonate, dodecyl alcohol polyoxyethylene ether sulfate, sodium dioctyl sulfosuccinate, N-oleoyl-N-methyl taurate, and lignin sulfonate.

5. A method for preparing the cathode material of a laminated aluminum electrolytic capacitor according to any one of claims 1 to 4, characterized in that: include: The metal foil is separated into an anode area and a cathode area by using a barrier adhesive, and a coupling agent layer, a metal oxide layer and a conductive polymer layer are sequentially formed on the cathode area of ​​the metal foil. The cathode area in which the coupling agent layer, the metal oxide layer and the conductive polymer layer are sequentially formed is the cathode material of the laminated aluminum electrolytic capacitor.

6. The method according to claim 5, characterized in that The step of forming the coupling agent layer comprises: placing the cathode region of the metal foil in a solution containing a coupling agent for a first immersion treatment to obtain the coupling agent layer; Optionally, the mass fraction of the coupling agent in the solution containing the coupling agent is 1 wt%-5 wt%.

7. The method according to any one of claims 5 to 6, characterized in that: The step of forming the metal oxide layer comprises: placing the cathode region of the metal foil forming the coupling agent layer in a solution containing a manganese salt and a thermal decomposition accelerator for a second immersion treatment, and performing a dehydration treatment and a thermal decomposition treatment to obtain the metal oxide layer; Optionally, the manganese salt includes at least one of manganese nitrate, potassium permanganate, and manganese carbonate; Optionally, the thermal decomposition accelerator includes at least one of ethylene glycol amine, titanium dioxide, and ammonium citrate; Optionally, the mass fraction of the manganese salt in the solution containing the manganese salt and the thermal decomposition accelerator is 50 wt % to 70 wt %; Optionally, the mass fraction of the thermal decomposition accelerator in the solution containing the manganese salt and the thermal decomposition accelerator is 2wt%-8wt%; Optionally, the temperature of the second impregnation treatment is 10°C-30°C; Optionally, the second immersion treatment time is 5 min-40 min; Optionally, the temperature of the dehydration treatment is 100°C-180°C; Optionally, the dehydration treatment time is 15 min-45 min; Optionally, the temperature of the thermal decomposition treatment is 200°C-400°C; Optionally, the thermal decomposition treatment time is 20 min-50 min; Optionally, the step of forming the conductive polymer layer comprises: The metal foil forming the metal oxide layer is used as an anode and placed in a solution containing a polymer monomer, an electrolyte and a surfactant to obtain the conductive polymer layer by electropolymerization; Optionally, the concentration of the polymer monomer in the solution containing the polymer monomer, electrolyte and surfactant is 0.2 mol / L-0.6 mol / L; Optionally, the concentration of the electrolyte in the solution containing the polymer monomer, electrolyte and surfactant is 0.1 mol / L-0.3 mol / L; Optionally, the concentration of the surfactant in the solution containing the polymer monomer, electrolyte and surfactant is 0.1 mol / L-0.3 mol / L; Optionally, the pH value of the solution containing the polymer monomer, electrolyte and surfactant is 2-6; Optionally, the electropolymerization satisfies at least one of the following conditions: The temperature of the electropolymerization is 0°C-25°C; The scanning voltage cycle range was 0 V–1.6 V; Scan speed: 20 mV / s -70 mV / s; The number of scanning circles is 10-50 circles; Optionally, the metal foil comprises a chemically formed foil.

8. An electrode foil, characterized in that include: An anode region and a cathode region, wherein the anode region and the cathode region are separated by a metal foil using a barrier adhesive, and the cathode region is selected from the laminated aluminum electrolytic capacitor cathode material according to any one of claims 1 to 4 or the laminated aluminum electrolytic capacitor cathode material prepared by the preparation method according to any one of claims 5 to 7; Optionally, the metal foil comprises a chemically formed foil; Optionally, the anode region is left untreated.

9. Use of the cathode material for a laminated aluminum electrolytic capacitor according to any one of claims 1 to 4, the cathode material for a laminated aluminum electrolytic capacitor prepared by the preparation method according to any one of claims 5 to 7, or the electrode foil according to claim 8 as an electrode material for a laminated aluminum electrolytic capacitor.

10. A laminated aluminum electrolytic capacitor, characterized in that: The cathode region of the electrode material of the laminated aluminum electrolytic capacitor comprises the laminated aluminum electrolytic capacitor cathode material according to any one of claims 1 to 4, or the laminated aluminum electrolytic capacitor cathode material obtained by the method according to any one of claims 5 to 7, or the electrode material of the laminated aluminum electrolytic capacitor comprises the electrode foil according to claim 8.

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