Conductive carbon paste, laminated capacitor and preparation method thereof

Abstract

The invention belongs to the technical field of electrode materials, and particularly relates to conductive carbon paste, a laminated capacitor and a preparation method of the laminated capacitor. The raw material of the conductive carbon paste comprises a fluorine-containing conductive material, and the fluorine-containing conductive material is a metal organic framework loaded fluorinated carbon nanotube compound. Compared with graphite, the conductivity of the conductive carbon paste is remarkably improved, the impedance is reduced, the loss is reduced, and the laminated capacitor applying the conductive carbon paste can pass a double-85 test.

Description

Technical Field

[0001] The invention belongs to the technical field of electrode materials, and in particular relates to a conductive carbon paste and a laminated capacitor and a preparation method thereof. Background Art

[0002] Laminated solid aluminum electrolytic capacitors are mainly used in notebook computer motherboards, servers and other fields. The main problem of domestic laminated capacitors is that they cannot pass the double 85 test. The so-called double 85 test is to place the product in an environment with a relative humidity of 85% and a temperature of 85°C for a period of time, and then test the various performance indicators of the laminated capacitor. After the double 85 test, the various performance indicators of the laminated capacitor deteriorate and fail, and cannot meet the qualified standards. The reason for the failure is: the conductive carbon paste currently used in laminated capacitors cannot be waterproof as a transition layer. In the double 85 test, water enters the capacitor core, causing the polymer layer to lose conductivity, which in turn causes the degradation of various performances of the laminated capacitor. At the same time, the existing conductive carbon paste uses graphite as a conductive material, and the conductivity of graphite is relatively low, which leads to a relatively large impedance and loss of the laminated capacitor.

[0003] To this end, the present invention is proposed. Summary of the invention

[0004] The main purpose of the present invention is to provide a conductive carbon paste and a laminated capacitor and a preparation method thereof. The conductivity of the conductive carbon paste in the present invention is significantly improved compared with graphite, the impedance is reduced, and the loss is reduced. The laminated capacitor using the conductive carbon paste of the present invention can pass the double 85 test.

[0005] In order to achieve the above objectives, the present invention provides the following technical solutions.

[0006] In a first aspect, the present invention provides a conductive carbon paste, wherein the raw material of the conductive carbon paste comprises a fluorine-containing conductive material, and the fluorine-containing conductive material is a metal organic framework-loaded fluorinated carbon nanotube composite.

[0007] In an embodiment of the present invention, the mass percentage of the fluorine-containing conductive material in the raw materials of the conductive carbon paste is 30wt% to 50wt%; the mass percentages of the raw materials in total are 100wt%.

[0008] In an embodiment of the present invention, the metal organic framework-supported fluorinated carbon nanotube composite is prepared from a metal organic framework material, fluorinated carbon nanotubes, a binder, and a second solvent;

[0009] Among them, the mass percentage of each component is:

[0010] Metal organic framework materials: 20wt% to 40wt%;

[0011] Fluorinated carbon nanotubes: 20wt% to 40wt%;

[0012] Binder: 10wt% to 30wt%;

[0013] Second solvent: balance;

[0014] The mass percentages of the various components add up to 100 wt%.

[0015] In an embodiment of the present invention, the metal organic framework material in the metal organic framework-loaded fluorinated carbon nanotube composite includes ZIF-1, ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-11, ZIF-12, ZIF-14, ZIF-20, ZIF-21, ZIF-22, ZIF-23, ZIF-60, ZIF-61, ZIF-62, ZIF-63, ZIF-64, ZIF-65, ZIF-66, ZIF-67, ZIF-68, ZIF-69, ZIF-70, ZIF-71, ZIF-72, ZIF-73, ZIF-74, ZIF-75, ZIF-76, ZIF-77, ZIF-78, ZIF-79, ZIF-80, ZIF-81, ZIF-82, ZIF-83, ZIF-84, ZIF-85, ZIF-86, ZIF-87, ZIF-88, ZIF-89, ZIF-90, ZIF-91, ZIF-92, ZIF-93, ZIF-10 One or more combinations of IF-61, ZIF-62, ZIF-64, ZIF-65, ZIF-67, ZIF-68, ZIF-69, ZIF-70, ZIF-73, ZIF-74, ZIF-75, ZIF-76, ZIF-77, ZIF-78, ZIF-79, ZIF-82, ZIF-90, ZIF-91, and ZIF-92; wherein ZIF is a zeolite imidazolate framework structure material.

[0016] In an embodiment of the present invention, the adhesive may be one or more combinations of PVP-K15, PVP-K30, PVP-K60, and PVP-K90; wherein PVP is polyvinyl pyrrolidone.

[0017] In an embodiment of the present invention, the second solvent may be one or more combinations of water, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, toluene, p-xylene, and cyclohexanone.

[0018] In an embodiment of the present invention, the raw materials of the conductive carbon paste further include at least one of a matrix polymer, a binder, a thickener, and a curing agent.

[0019] Preferably, in the conductive carbon paste, by mass percentage, the mass percentage of the base polymer is 8wt% to 13wt%, the mass percentage of the binder is 0.5wt% to 1.5wt%, the mass percentage of the thickener is 1.5wt% to 3.0wt%, and the mass percentage of the curing agent is 1.5wt% to 2.5wt%.

[0020] In an embodiment of the present invention, the raw materials of the conductive carbon paste further include at least one of a surfactant, a defoaming agent, an acid-base regulator, and a first solvent.

[0021] Preferably, in the conductive carbon paste, in terms of mass percentage, the mass percentage of the surfactant is 0.5wt% to 1.5wt%, the mass percentage of the defoaming agent is 0.5wt% to 1.0wt%, the mass percentage of the acid-base regulator is 0.5wt% to 1.0wt%, and the mass percentage of the first solvent is 40wt% to 60wt%.

[0022] In an embodiment of the present invention, the matrix polymer may be one or more combinations of polyurethane resin, polysiloxane resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutylene resin, epoxy resin, phenolic resin, acrylic resin, and polyvinyl chloride resin.

[0023] In an embodiment of the present invention, the first solvent includes one or more combinations of water, ethanol, propanol, isopropanol, n-butanol, tert-butanol, n-hexanol, N,N-dimethylformamide, N-methylpyrrolidone, toluene, p-xylene, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, 2-phenoxyethanol, cyclohexanone, 1,2-propylene glycol, ethylene glycol, and ethylene glycol carbonate.

[0024] In an embodiment of the present invention, the binder includes one or more combinations of polyvinylidene fluoride, modified silane polymer, polyurethane, silicone, hydroxypropyl methylcellulose, water glass, rubber, starch, protein, dextrin, animal glue, shellac, hide glue, and rosin.

[0025] In an embodiment of the present invention, the surfactant includes one or more combinations of fatty acid glycerides, sucrose fatty acid esters, fatty acid sorbitan, polysorbate, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene-polyoxypropylene copolymers, betaine-type zwitterionic surfactants, amino acid-type zwitterionic surfactants, benzalkonium chloride, benzalkonium bromide, dioctyl sodium succinate sulfonate, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium stearate, potassium stearate, calcium stearate, and triethanolamine soap.

[0026] In an embodiment of the present invention, the thickener includes titanium dioxide, hydroxyethyl cellulose, sodium chloride, potassium chloride, ammonium chloride, monoethanolamine chloride, diethanolamine chloride, sodium sulfate, sodium phosphate, disodium phosphate, pentasodium triphosphate, lauryl alcohol, myristyl alcohol, C12-16 alcohol, decanol, hexanol, capryl alcohol, cetyl alcohol, stearyl alcohol, lauric acid, C18-36 acid, linoleic acid, linolenic acid, myristic acid, stearic acid, coconut diethanolamide, coconut monoethanolamide, coconut monoisopropanolamide, cocamide, lauroyl-linoleyl diethanolamide, lauroyl-cardamom One or more combinations of acyl diethanolamide, isostearyl diethanolamide, linoleyl diethanolamide, myristic diethanolamide, myristic monoethanolamide, oil diethanolamide, palm monoethanolamide, castor oil monoethanolamide, sesame diethanolamide, soybean diethanolamide, stearyl diethanolamide, stearyl monoethanolamide, stearyl monoethanolamide stearate, stearamide, tallow monoethanolamide, wheat germ diethanolamide, polyethylene glycol -3 lauramide, PEG-4 oleamide, cetyl alcohol polyoxyethylene ether, isocetyl alcohol polyoxyethylene ether, and lauryl alcohol polyoxyethylene ether.

[0027] In an embodiment of the present invention, the curing agent includes one or more combinations of epoxy resin curing agent, amine curing agent, polyurethane curing agent, silicone curing agent, ketone alcohol curing agent, alkyd curing agent, and aluminum oxide curing agent.

[0028] In an embodiment of the present invention, the defoamer includes one or more combinations of silicone defoamers, polyether defoamers, mineral oil defoamers, polyether-modified polysiloxane defoamers, high carbon alcohol defoamers, silicone oil defoamers, polyvinyl alcohol defoamers, phosphate defoamers, and ester defoamers.

[0029] In an embodiment of the present invention, the acid-base regulator includes one or more combinations of sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, copper hydroxide, iron hydroxide, lead hydroxide, cobalt hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, ammonia water, triethylamine, sodium methoxide, potassium ethoxide, potassium tert-butoxide, and pyridine.

[0030] In an embodiment of the present invention, the metal organic framework-supported fluorinated carbon nanotube composite is prepared by the following process:

[0031] The second solvent, the binder, the acidified fluorinated carbon nanotubes and the metal organic framework material are mixed, stirred evenly, heated to 200°C to 300°C for reaction for 5h to 15h, cooled to room temperature, and centrifuged to obtain a solid product. The solid product is ultrasonically cleaned and dried at 60°C to 100°C for 6h to 10h to obtain a metal organic framework-loaded fluorinated carbon nanotube composite.

[0032] The second aspect of the present invention provides a method for preparing the conductive carbon paste according to the first aspect of the present invention, comprising the following steps:

[0033] Mixing the raw materials of the conductive carbon paste and stirring and dispersing them to obtain a dispersion;

[0034] The dispersion is sequentially ground, filtered, pH adjusted and centrifuged to obtain the conductive carbon slurry.

[0035] Preferably, the pH is adjusted to 7-9; the average particle size of the filtrate obtained after filtration is preferably 40 μm-60 μm.

[0036] The third aspect of the present invention provides a method for preparing a stacked capacitor, which includes coating the conductive carbon paste described in the first aspect of the present invention or the conductive carbon paste prepared by the preparation method described in the second aspect of the present invention on the cathode area of ​​the chemically formed foil before preparing the lead-out layer to form a transition layer of the stacked capacitor.

[0037] In an embodiment of the present invention, the conductive carbon paste is coated on the cathode region of the formed foil by dipping, blade coating or screen printing.

[0038] Preferably, the conductive carbon paste has a viscosity of 1±0.2 dPa·s and a solid content of 30% to 50%.

[0039] In a fourth aspect, the present invention provides a multilayer capacitor, wherein the transition layer of the multilayer capacitor comprises the conductive carbon paste described in the first aspect of the present invention or the conductive carbon paste prepared by the preparation method described in the second aspect of the present invention;

[0040] Alternatively, the multilayer capacitor is manufactured by the manufacturing method described in the third aspect of the present invention.

[0041] Compared with the prior art, the present invention achieves the following technical effects:

[0042] The conductivity of the conductive carbon paste of the present invention is significantly improved compared with graphite, and the impedance and loss are reduced.

[0043] The conductive carbon paste of the present invention is used as a transition layer of the stacked capacitor, so that the waterproof performance of the stacked capacitor is significantly improved, and can pass the double 85% test, thereby improving the comprehensive performance and extending the service life.

[0044] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention, it can be implemented according to the contents of the specification. In order to make the above and other purposes, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are listed below. DETAILED DESCRIPTION

[0045] Below, embodiments of the present invention will be specifically described. However, it should be understood that these descriptions are exemplary only and are not intended to limit the scope of the present invention. In addition, in the following description, descriptions of known structures and technologies are omitted to avoid unnecessary confusion of the concept of the present invention.

[0046] In the description of the embodiments of the present invention, technical terms such as "first" and "second" are only used to distinguish different objects and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features.

[0047] The room temperature in the embodiment of the present invention is 20°C to 30°C.

[0048] The first aspect of the present invention provides a conductive carbon paste. The raw material of the conductive carbon paste includes a fluorine-containing conductive material. The fluorine-containing conductive material is a metal organic framework-loaded fluorinated carbon nanotube composite.

[0049] The present invention adopts a metal organic framework loaded fluorinated carbon nanotube composite as the conductive material of the conductive carbon paste, so that the conductivity of the conductive carbon paste is significantly improved compared with graphite, and the impedance is reduced and the loss is reduced.

[0050] The conductive carbon paste of the present invention is applied to a laminated capacitor, such as a transition layer of a laminated solid aluminum electrolytic capacitor, so that the waterproof performance of the laminated capacitor is significantly improved, and the capacitor can pass a double 85% test, thereby improving the overall performance and extending the service life.

[0051] In the embodiment of the present invention, the mass percentage of the fluorine-containing conductive material in the raw materials of the conductive carbon paste is 30wt% to 50wt%; the mass percentages of the raw materials in total are 100wt%.

[0052] In the conductive carbon paste provided by the present invention, the mass percentage of the fluorine-containing conductive material can be a value in the interval composed of any two values ​​in the above range, for example, it can be 30wt% to 40wt%, or it can be 40wt% to 50wt%, and so on. In the conductive carbon paste provided by the present invention, the mass percentage of the fluorine-containing conductive material can also be 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt% or any value that meets the above range.

[0053] In an embodiment of the present invention, the raw materials of the conductive carbon paste also include a matrix polymer.

[0054] In the embodiment of the present invention, in the conductive carbon paste, the mass percentage of the matrix polymer is 8wt% to 13wt% by mass.

[0055] In the conductive carbon paste provided by the present invention, the mass percentage of the matrix polymer can be a value in the interval formed by any two values ​​in the above range, for example, it can be 8wt% to 10wt%, or it can be 9wt% to 13wt%, and so on. In the conductive carbon paste provided by the present invention, the mass percentage of the matrix polymer can also be one of 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt% or any value that meets the above range.

[0056] In an embodiment of the present invention, the raw materials of the conductive carbon paste also include a binder.

[0057] In an embodiment of the present invention, in the conductive carbon paste, the mass percentage of the binder may be 0.5 wt % to 1.5 wt %.

[0058] In the conductive carbon paste provided by the present invention, the mass percentage of the binder can be a value in the interval formed by any two values ​​in the above range, for example, it can be 0.5wt% to 1.0wt%, or it can be 0.8wt% to 1.5wt%, and so on. In the conductive carbon paste provided by the present invention, the mass percentage of the binder can also be one of 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, or any value that meets the above range.

[0059] In an embodiment of the present invention, the raw materials of the conductive carbon paste also include a thickener.

[0060] In the embodiment of the present invention, in the conductive carbon paste, the mass percentage of the thickener may be 1.5 wt % to 3.0 wt %.

[0061] In the conductive carbon paste provided by the present invention, the mass percentage of the thickener can be a value in the interval composed of any two values ​​in the above range, for example, it can be 1.5wt% to 2.0wt%, or it can be 1.8wt% to 3.0wt%, and so on. In the conductive carbon paste provided by the present invention, the mass percentage of the thickener can also be one of 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2.0wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3.0wt% or any value that meets the above range.

[0062] In an embodiment of the present invention, the raw materials of the conductive carbon paste also include a curing agent.

[0063] In an embodiment of the present invention, in the conductive carbon paste, the mass percentage of the curing agent may be 1.5 wt % to 2.5 wt %.

[0064] In the conductive carbon paste provided by the present invention, the mass percentage of the curing agent can be a value in the interval formed by any two values ​​in the above range, for example, it can be 1.5wt% to 2.0wt%, or it can be 1.8wt% to 2.5wt%, and so on. In the conductive carbon paste provided by the present invention, the mass percentage of the curing agent can also be one of 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2.0wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt% or any value that meets the above range.

[0065] In an embodiment of the present invention, the raw materials of the conductive carbon paste further include a surfactant, a defoaming agent, an acid-base regulator and a first solvent.

[0066] In an embodiment of the present invention, in the conductive carbon paste, in terms of mass percentage, the mass percentage of the surfactant is 0.5wt% to 1.5wt%, the mass percentage of the defoaming agent is 0.5wt% to 1.0wt%, the mass percentage of the acid-base regulator is 0.5wt% to 1.0wt%, and the mass percentage of the first solvent is 40wt% to 60wt%.

[0067] In the conductive carbon paste provided by the present invention, the mass percentage of the surfactant can be a value in the interval formed by any two values ​​in the above range, for example, it can be 0.5wt% to 1.0wt%, or it can be 0.8wt% to 1.5wt%, and so on. In the conductive carbon paste provided by the present invention, the mass percentage of the surfactant can also be one of 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, or any value that meets the above range.

[0068] In the conductive carbon paste provided by the present invention, the mass percentage of the defoaming agent can be a value in the interval formed by any two values ​​in the above range, for example, it can be 0.5wt% to 0.8wt%, or it can be 0.8wt% to 1.0wt%, and so on. In the conductive carbon paste provided by the present invention, the mass percentage of the defoaming agent can also be one of 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt% or any value that meets the above range.

[0069] In the conductive carbon paste provided by the present invention, the mass percentage of the acid-base regulator can be a value in the interval formed by any two values ​​in the above range, for example, it can be 0.5wt% to 0.8wt%, or it can be 0.8wt% to 1.0wt%, and so on. In the conductive carbon paste provided by the present invention, the mass percentage of the acid-base regulator can also be one of 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt% or any value that meets the above range.

[0070] In the conductive carbon paste provided by the present invention, the mass percentage of the first solvent can be a value in the interval composed of any two values ​​in the above range, for example, it can be 40wt% to 50wt%, or it can be 45wt% to 60wt%, and so on. In the conductive carbon paste provided by the present invention, the mass percentage of the first solvent can also be one of 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, 51wt%, 52wt%, 53wt%, 54wt%, 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt% or any value that meets the above range.

[0071] In an embodiment of the present invention, the metal organic framework material in the metal organic framework-supported fluorinated carbon nanotube composite includes ZIF-1, ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-11, ZIF-12, ZIF-14, ZIF-20, ZIF-21, ZIF-22, ZIF-23, ZIF-60, ZIF-61, ZIF-62, ZIF-63, ZIF-64, ZIF-65, ZIF-66, ZIF-67, ZIF-68, ZIF-69, ZIF-70, ZIF-71, ZIF-72, ZIF-73, ZIF-74, ZIF-75, ZIF-76, ZIF-77, ZIF-78, ZIF-79, ZIF-80, ZIF-81, ZIF-82, ZIF-83, ZIF-84, ZIF-85, ZIF-86, ZIF-87, ZIF-88, ZIF-89, ZIF-90, ZIF-91, ZIF-92, ZIF-93, ZIF-10 One or more combinations of F-61, ZIF-62, ZIF-64, ZIF-65, ZIF-67, ZIF-68, ZIF-69, ZIF-70, ZIF-73, ZIF-74, ZIF-75, ZIF-76, ZIF-77, ZIF-78, ZIF-79, ZIF-82, ZIF-90, ZIF-91, and ZIF-92; wherein ZIF is a zeolite imidazolate framework structure material.

[0072] In an embodiment of the present invention, the matrix polymer may be one or more combinations of polyurethane resin, polysiloxane resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutylene resin, epoxy resin, phenolic resin, acrylic resin, and polyvinyl chloride resin.

[0073] In an embodiment of the present invention, the first solvent can be one or more combinations of water, ethanol, propanol, isopropanol, n-butanol, tert-butanol, n-hexanol, N,N-dimethylformamide, N-methylpyrrolidone, toluene, p-xylene, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, 2-phenoxyethanol, cyclohexanone, 1,2-propylene glycol, ethylene glycol, and ethylene glycol carbonate.

[0074] In an embodiment of the present invention, the binder may be one or more combinations of polyvinylidene fluoride, modified silane polymer, polyurethane, silicone, hydroxypropyl methylcellulose (HPMC), water glass, rubber, starch, protein, dextrin, animal glue, shellac, hide glue, and rosin.

[0075] In an embodiment of the present invention, the surfactant can be one or more combinations of fatty acid glyceride, sucrose fatty acid ester, fatty acid sorbitan, polysorbate, polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene-polyoxypropylene copolymer, betaine type zwitterionic surfactant, amino acid type zwitterionic surfactant, benzalkonium chloride, benzalkonium bromide, dioctyl sodium succinate, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium stearate, potassium stearate, calcium stearate, and triethanolamine soap.

[0076] In an embodiment of the present invention, the thickener can be titanium dioxide, hydroxyethyl cellulose, sodium chloride, potassium chloride, ammonium chloride, monoethanolamine chloride, diethanolamine chloride, sodium sulfate, sodium phosphate, disodium phosphate, pentasodium triphosphate, lauryl alcohol, myristyl alcohol, C12-16 alcohol, decanol, hexanol, capryl alcohol, cetyl alcohol, stearyl alcohol, lauric acid, C18-36 acid, linoleic acid, linolenic acid, myristic acid, stearic acid, coconut diethanolamide, coconut monoethanolamide, coconut monoisopropanolamide, cocamide, lauroyl-linoleoyl diethanolamide, lauroyl-myristoyl diethyl One or more combinations of alcohol amide, isostearyl diethanolamide, linoleyl diethanolamide, myristic diethanolamide, myristic monoethanolamide, oil diethanolamide, palm monoethanolamide, castor oil monoethanolamide, sesame diethanolamide, soybean diethanolamide, stearyl diethanolamide, stearyl monoethanolamide, stearyl monoethanolamide stearate, stearamide, tallow monoethanolamide, wheat germ diethanolamide, polyethylene glycol (PEG) -3 lauramide, PEG-4 oleamide, cetyl alcohol polyoxyethylene ether, isocetyl alcohol polyoxyethylene ether, and lauryl alcohol polyoxyethylene ether.

[0077] In an embodiment of the present invention, the curing agent may be one or more combinations of epoxy resin curing agent, amine curing agent, polyurethane curing agent, silicone curing agent, ketone alcohol curing agent, alkyd curing agent, and aluminum oxide curing agent;

[0078] In an embodiment of the present invention, the defoamer can be one or more combinations of silicone defoamers, polyether defoamers, mineral oil defoamers, polyether-modified polysiloxane defoamers, high carbon alcohol defoamers, silicone oil defoamers, polyvinyl alcohol defoamers, phosphate defoamers, and ester defoamers.

[0079] In an embodiment of the present invention, the acid-base regulator can be one or more combinations of sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, copper hydroxide, iron hydroxide, lead hydroxide, cobalt hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, ammonia water, triethylamine, sodium methoxide, potassium ethoxide, potassium tert-butoxide, and pyridine.

[0080] In an embodiment of the present invention, the metal organic framework-supported fluorinated carbon nanotube composite is prepared from a metal organic framework material, fluorinated carbon nanotubes, a binder, and a second solvent;

[0081] Among them, the mass percentage of each component is:

[0082] Metal organic framework material: 20wt% to 40wt%; fluorinated carbon nanotubes: 20wt% to 40wt%; adhesive: 10wt% to 30wt%; second solvent: balance; the total mass percentage of each component is 100%.

[0083] In the metal organic framework loaded fluorinated carbon nanotube composite provided by the present invention, the mass percentage of the metal organic framework material can be a value of an interval composed of any two values ​​in the above interval, for example, it can be 20wt% to 30wt%, or it can be 30wt% to 40wt%, and so on. In the metal organic framework loaded fluorinated carbon nanotube composite provided by the present invention, the mass percentage of the metal organic framework material can also be 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt% or any value that meets the above range value.

[0084] In the metal organic framework supported fluorinated carbon nanotube composite provided by the present invention, the mass percentage of the fluorinated carbon nanotubes can be a value of an interval composed of any two values ​​in the above interval, for example, it can be 20wt% to 30wt%, or it can be 30wt% to 40wt%, and so on. In the metal organic framework supported fluorinated carbon nanotube composite provided by the present invention, the mass percentage of the fluorinated carbon nanotubes can also be 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt% or any value that meets the above range.

[0085] In an embodiment of the present invention, the second solvent may be one or more combinations of water, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, toluene, p-xylene, and cyclohexanone.

[0086] In the metal organic framework supported fluorinated carbon nanotube composite provided by the present invention, the mass percentage of the binder can be a value of an interval composed of any two values ​​in the above interval, for example, it can be 10wt% to 20wt%, or it can be 20wt% to 30wt%, and so on. In the metal organic framework supported fluorinated carbon nanotube composite provided by the present invention, the mass percentage of the binder can also be 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt% or any value that meets the above range value.

[0087] In an embodiment of the present invention, the adhesive may be one or more combinations of PVP-K15, PVP-K30, PVP-K60, and PVP-K90; wherein PVP is polyvinyl pyrrolidone.

[0088] In an embodiment of the present invention, the metal organic framework-supported fluorinated carbon nanotube composite is prepared by the following process:

[0089] The second solvent, the binder, the acidified fluorinated carbon nanotubes and the metal organic framework material are mixed, stirred until uniform, heated to 200°C to 300°C for reaction for 5h to 15h, cooled to room temperature, and centrifuged to obtain a solid product. The solid product is ultrasonically cleaned and dried at 60°C to 100°C for 6h to 10h to obtain the metal organic framework-loaded fluorinated carbon nanotube composite.

[0090] The second aspect of the present invention provides a method for preparing the conductive carbon paste described in the first aspect of the present invention.

[0091] The preparation method of the conductive carbon paste in the present invention is carried out according to the following steps:

[0092] (1) A fluorine-containing conductive material, a base polymer, a first solvent, a surfactant, a binder, a thickener, a curing agent, a defoaming agent and an acid-base regulator are mixed and stirred to obtain a dispersion.

[0093] In the embodiment of the present invention, the raw materials are added according to the mass percentage of each raw material, and the materials are stirred and dispersed to obtain a uniform dispersion.

[0094] In some embodiments of the present invention, the stirring and dispersing speed may be 100 to 200 rpm, and the dispersing time may be 15 to 60 minutes.

[0095] The stirring and dispersing speed provided by the present invention can be the value of the interval composed of any two values ​​in the above interval, such as 100 to 150 rpm, or 150 to 200 rpm, and so on. The stirring and dispersing speed provided by the present invention can be 100 rpm, 110 rpm, 120 rpm, 130 rpm, 140 rpm, 150 rpm, 160 rpm, 170 rpm, 180 rpm, 190 rpm, 200 rpm. The dispersion time provided by the present invention can be the value of the interval composed of any two values ​​in the above interval, such as 15 to 40 minutes, or 30 to 60 minutes, and so on. The dispersion time provided by the present invention can be 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes.

[0096] (2) Grinding, filtering, adjusting the pH value and centrifugation dispersion of the dispersion in sequence to obtain the conductive carbon slurry described in the first aspect.

[0097] In some embodiments of the present invention, the dispersion obtained in step (1) is transferred to a three-roll mill for grinding, so that the materials are further mixed and uniformly mixed, and the fineness of the materials is further reduced.

[0098] In some embodiments of the present invention, the grinding speed may be 50 to 120 rpm, and the grinding time may be 60 to 120 minutes.

[0099] The grinding speed provided by the present invention can be a value of an interval composed of any two values ​​in the above interval, for example, it can be 50 to 100 rpm, or 80 to 120 rpm, and so on. The grinding speed provided by the present invention can be 50 rpm, 60 rpm, 70 rpm, 80 rpm, 90 rpm, 100 rpm, 110 rpm, and 120 rpm. The grinding time provided by the present invention can be a value of an interval composed of any two values ​​in the above interval, for example, it can be 60 to 100 minutes, or 80 to 120 minutes, and so on. The grinding time provided by the present invention can be 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes,

[0100] 110 minutes, 120 minutes.

[0101] In some embodiments of the present invention, the average particle size of the ground material is in the range of 40 μm to 80 μm.

[0102] The average particle size of the ground material provided by the present invention can be a value of an interval consisting of any two values ​​in the above interval, for example, it can be 40-60 μm, or 60-80 μm, and so on. The average particle size of the ground material provided by the present invention can be 40 μm, 50 μm, 60 μm, 70 μm, or 80 μm.

[0103] The ground material is filtered to remove components with larger particle sizes and obtain components that meet size requirements.

[0104] In some embodiments of the present invention, the average particle size of the filtrate obtained after filtration may be in the range of 40 μm to 60 μm.

[0105] The average particle size of the filtrate obtained after filtration provided by the present invention can be a value of an interval composed of any two values ​​in the above interval, for example, it can be 40μm to 50μm, or it can be 50μm to 60μm, and so on. The average particle size of the filtrate obtained after filtration provided by the present invention can also be 40μm, 41μm, 42μm, 43μm, 44μm, 45μm, 46μm, 47μm, 48μm, 49μm, 50μm, 51μm, 52μm, 53μm, 54μm, 55μm, 56μm, 57μm, 58μm, 59μm, 60μm or any value that meets the above range value.

[0106] The pH of the filtrate or the dispersion obtained after filtration is adjusted, for example, by adding pyridine to adjust the pH to 7-9.

[0107] The pH value of the pH-adjusted material provided by the present invention is one of 7, 8, 9 or any value within the above range.

[0108] Finally, a centrifuge is used to centrifugally disperse the pH-adjusted material so that the material is evenly dispersed, thereby obtaining a conductive carbon slurry.

[0109] In some embodiments of the present invention, the centrifugal speed may be 5000 to 30000 rpm, and the centrifugal time may be 5 to 15 minutes.

[0110] The centrifugal speed provided by the present invention can be the value of the interval composed of any two values ​​in the above interval, such as 5000-20000 rpm, or 10000-30000 rpm, and so on. The grinding speed provided by the present invention can be 5000 rpm, 10000 rpm, 15000 rpm, 20000 rpm, 25000 rpm, 30000 rpm. The centrifugal time provided by the present invention can be the value of the interval composed of any two values ​​in the above interval, such as 5-10 minutes, or 8-15 minutes, and so on. The centrifugal time provided by the present invention can be 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes.

[0111] The third aspect of the present invention provides a method for preparing a stacked capacitor, the key of which is to apply the conductive carbon paste described in the first aspect of the present invention or the conductive carbon paste prepared by the preparation method described in the second aspect of the present invention to the transition layer of the stacked capacitor.

[0112] The present invention is described by taking a laminated solid aluminum electrolytic capacitor as an example. Before preparing the lead-out layer, the conductive carbon paste described in the present invention is coated on the cathode region of the formed foil to form a transition layer of the laminated capacitor.

[0113] As some embodiments of the present invention, the conductive carbon paste may be coated on the cathode region of the formed foil by dipping, blade coating or screen printing.

[0114] As some embodiments of the present invention, the viscosity of the conductive carbon paste may be 1±0.2 dPa·s, and the solid content may be 30% to 50%.

[0115] The solid content of the conductive carbon paste provided by the present invention can be a value in the interval composed of any two values ​​in the above range, for example, it can be 30% to 40%, or 40% to 50%, and so on. The solid content of the conductive carbon paste provided by the present invention can also be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50% or any value that meets the above range.

[0116] In some embodiments of the present invention, coating the conductive carbon slurry on the cathode region of the formed foil by impregnation includes:

[0117] The cathode area of ​​the formed foil is immersed in the conductive carbon slurry with a solid content of 30wt% to 50wt% and a viscosity of 1±0.2dPa·s provided by the present invention for 5s to 20s, slowly pulled out, naturally dried for 5min to 20min, and then dried at a temperature of 100℃ to 135℃ for 15min to 45min to solidify.

[0118] In some embodiments of the present invention, a method for preparing a multilayer capacitor is also provided:

[0119] S1 Pretreatment of chemical foil: Apply a layer of barrier glue on the cut aluminum foil, then cure it at 130℃~150℃ for 30min~60min, then perform chemical repair for 10min~20min, and finally treat the surface of the chemical aluminum foil with a coupling agent aqueous solution, first dry it naturally for 10min~20min, and then dry it at a high temperature of 120℃~140℃ for 10min~15min.

[0120] Preparation of S2 cathode layer: Immerse the cathode area of ​​the pre-treated chemical foil in a 3,4-ethylenedioxythiophene monomer solution at a temperature of 20°C to 30°C for 5min to 10min, then take it out and dry it at a temperature of 100°C to 110°C for 20min to 40min, then immerse the cathode area of ​​the chemical foil in an iron p-toluenesulfonate oxidant solution at a temperature of 15°C to 25°C for 5min to 10min, and after taking out the aluminum foil, dry it at a temperature of 100°C to 120°C for 15min to 30min. Wash and dry the chemical foil that has completed the polymerization reaction with deionized water to complete a polymerization cycle. Repeat the above polymerization cycle 20 to 25 times.

[0121] Preparation of S3 transition layer: The cathode area of ​​the chemically formed foil obtained in the above step is immersed in the conductive carbon slurry with a solid content of 30wt% to 50wt% and a viscosity of 1±0.2dPa·s provided by the present invention for 5s to 20s, slowly pulled out, naturally dried for 5min to 20min, and then dried at a temperature of 100℃ to 135℃ for 15min to 45min to solidify.

[0122] Preparation of S4 lead-out layer: The silver paste is coated on the surface of the cathode area of ​​the formed foil impregnated with conductive graphite in step S3 by the immersion-pulling method. The solid content of the silver paste is 50wt% to 70wt%, and the viscosity is 1dPa·s to 1.15dPa·s. It is dried at a temperature of 130℃ to 150℃ for 20min to 40min to solidify to obtain a single capacitor.

[0123] S5 battery cell preparation: The prepared single capacitor is welded through multiple layers to obtain a battery cell, and then the battery cell is heat cured at a temperature of 130℃ to 150℃ for 30min to 60min, and then the battery cell is plastic-sealed to obtain a packaged product. The plastic-sealed capacitor is cut and bent to obtain a complete laminated solid aluminum electrolytic capacitor.

[0124] A fourth aspect of the present invention provides a multilayer capacitor, wherein the transition layer of the multilayer capacitor comprises the conductive carbon paste described in the first aspect or the conductive carbon paste prepared by the preparation method described in the second aspect;

[0125] Alternatively, the multilayer capacitor is manufactured by the manufacturing method described in the third aspect of the present invention.

[0126] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The experimental reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples, etc., can all be purchased on the market or can be obtained by existing methods; the amounts of the experimental reagents, unless otherwise specified, are the amounts of reagents used in conventional experimental operations; the experimental methods, unless otherwise specified, are all conventional methods.

[0127] The chemical reagents used in the specification and examples of the present invention include any conventional models or types in the art, and the present invention does not impose any special limiting requirements.

[0128] Example 1

[0129] Preparation of metal-organic framework ZIF-8 loaded with fluorinated carbon nanotubes composite (ZIF-8@F-CNTs)

[0130] 300 mL of a mixture of N-methylpyrrolidone and water was added to a 1000 mL stainless steel reactor, stirring was started and the speed was adjusted to 50 rpm, 10 g of polyvinylpyrrolidone (PVP-K50) was added to the mixture, 30 g of fluorinated carbon nanotubes acidified with trifluoroacetic anhydride / hydrogen peroxide at room temperature and 30 g of metal organic framework material ZIF-8 were added to the reactor in batches, reacted at room temperature for 1 h, then heated to 260 ° C and continued to react for 6 h, cooled naturally to room temperature, and centrifuged to obtain a solid product. The solid product was ultrasonically cleaned with ethanol, then ultrasonically cleaned with pure water, and dried at 80 ° C for 8 hours to obtain ZIF-8@F-CNTs. The monomer structure of the metal organic framework material ZIF-8 is shown in formula (1).

[0131]

[0132] Preparation of conductive carbon paste (1)

[0133] The weight percentage of each raw material is as follows: ZIF-8@F-CNTs as a conductive material, with a weight percentage of 30wt%; water as a solvent, with a weight percentage of 52wt%; polyetheretherketone as a matrix polymer, with a weight percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a weight percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a weight percentage of 1.5wt%; titanium dioxide as a thickener, with a weight percentage of 3wt%; epoxy resin as a curing agent, with a weight percentage of 1.5wt%; silicone as a defoaming agent, with a weight percentage of 0.5wt%; pyridine as an acid-base regulator, with a weight percentage of 1wt%.

[0134] Preparation of conductive carbon slurry (1): (1) ZIF-8@F-CNTs, water, polyetheretherketone, sodium dodecylbenzene sulfonate, polyvinylidene fluoride, titanium dioxide, epoxy resin and silicone are added according to the mass percentage, and the materials are stirred and dispersed by a planetary mixer at a stirring and dispersing speed of 150 rpm for 30 minutes to obtain a uniform dispersion; (2) The dispersion is transferred to a three-roll mill for grinding at a grinding speed of 80 rpm for 100 minutes to further mix the materials and further reduce the average particle size of the materials to below 80 μm; the materials are filtered to remove components with larger particle sizes to obtain a filtrate with an average particle size of 50 μm; pyridine is added to adjust the pH of the materials to 8; and finally, a centrifugal dispersion is performed at a centrifugal speed of 20,000 rpm for 10 minutes to obtain a uniform dispersion to obtain a conductive carbon slurry (1).

[0135] Preparation of laminated solid aluminum electrolytic capacitors

[0136] S1 Pretreatment of chemical foil: Apply a layer of barrier glue on the cut aluminum foil, then cure it at 150°C for 30 minutes, then perform chemical repair for 10 minutes, and finally treat the surface of the chemical aluminum foil with a coupling agent aqueous solution, first dry it naturally for 20 minutes, and then dry it at 120°C for 15 minutes.

[0137] Preparation of S2 cathode layer: The cathode area of ​​the chemical foil is immersed in a 3,4-ethylenedioxythiophene monomer solution at a temperature of 20°C for 5 minutes, then taken out and dried at a temperature of 110°C for 40 minutes, and then the cathode area of ​​the chemical foil is immersed in an iron p-toluenesulfonate oxidant solution at a temperature of 25°C for 5 minutes. After the aluminum foil is taken out, it is dried at a temperature of 120°C for 30 minutes. The chemical foil that has completed the polymerization reaction is washed with deionized water and dried to complete a polymerization cycle. Repeat the above polymerization cycle 20 times.

[0138] Preparation of S3 transition layer: The cathode area of ​​the chemically formed foil obtained above was immersed in a conductive carbon slurry (1) with a solid content of 30wt% and a viscosity of 1.1dPa·s for 10s, slowly pulled out, naturally dried for 10min, and then dried at 115°C for 25min to solidify.

[0139] Preparation of S4 lead-out layer: The silver paste is coated on the surface of the cathode area of ​​the above-mentioned electroplated foil impregnated with conductive graphite by the immersion-pulling method. The solid content of the silver paste is 70wt% and the viscosity is 1.15dPa·s. It is dried at 150°C for 20 minutes to solidify to obtain a single capacitor.

[0140] S5 cell preparation: The prepared single capacitor is welded through multiple layers to obtain a cell, and then the cell is heat cured at 150°C for 30 minutes, and then the cell is plastic-sealed to obtain a packaged product. The plastic-sealed capacitor is cut and bent to obtain a complete laminated solid aluminum electrolytic capacitor.

[0141] Example 2

[0142] The difference between Example 2 and Example 1 is that the metal organic framework material ZIF-8 is replaced with ZIF-67 to obtain a metal organic framework ZIF-67 loaded fluorinated carbon nanotube composite (ZIF-67@F-CNTs). The raw materials of the conductive carbon paste (2) are as follows in terms of mass percentage: ZIF-67@F-CNTs as a conductive material, with a mass percentage of 30wt%; water as a solvent, with a mass percentage of 52wt%; polyetheretherketone as a matrix polymer, with a mass percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a mass percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a mass percentage of 1.5wt%; titanium dioxide as a thickener, with a mass percentage of 3wt%; epoxy resin as a curing agent, with a mass percentage of 1.5wt%; silicone as a defoaming agent, with a mass percentage of 0.5wt%; pyridine as an acid-base regulator, with a mass percentage of 1wt%.

[0143] The monomer structure of the metal organic framework material ZIF-67 is shown in formula (2).

[0144]

[0145] The preparation methods of the metal organic framework ZIF-67 loaded fluorinated carbon nanotube composite (ZIF-67@F-CNTs), conductive carbon paste (2) and laminated solid aluminum electrolytic capacitor in Example 2 are the same as those in Example 1.

[0146] Example 3

[0147] The difference between Example 3 and Example 1 is that the metal organic framework material ZIF-8 is replaced with ZIF-14 to obtain a metal organic framework ZIF-14 loaded fluorinated carbon nanotube composite (ZIF-14@F-CNTs). Among them, the raw materials of the conductive carbon paste (3) are as follows in terms of mass percentage: ZIF-14@F-CNTs as a conductive material, with a mass percentage of 30wt%; water as a solvent, with a mass percentage of 52wt%; polyetheretherketone as a matrix polymer, with a mass percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a mass percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a mass percentage of 1.5wt%; titanium dioxide as a thickener, with a mass percentage of 3wt%; epoxy resin as a curing agent, with a mass percentage of 1.5wt%; silicone as a defoaming agent, with a mass percentage of 0.5wt%; pyridine as an acid-base regulator, with a mass percentage of 1wt%.

[0148] The monomer structure of the metal organic framework material ZIF-14 is shown in formula (3).

[0149]

[0150] The preparation methods of the metal organic framework ZIF-14 loaded fluorinated carbon nanotube composite (ZIF-14@F-CNTs), conductive carbon paste (3) and laminated solid aluminum electrolytic capacitor in Example 3 are the same as those in Example 1.

[0151] Example 4

[0152] The difference between Example 4 and Example 1 is that the metal organic framework material ZIF-8 is replaced with ZIF-62 to obtain a metal organic framework ZIF-62 loaded fluorinated carbon nanotube composite (ZIF-62@F-CNTs). Among them, the raw materials of the conductive carbon paste (4) are as follows in terms of mass percentage: ZIF-62@F-CNTs as a conductive material, with a mass percentage of 30wt%; water as a solvent, with a mass percentage of 52wt%; polyetheretherketone as a matrix polymer, with a mass percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a mass percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a mass percentage of 1.5wt%; titanium dioxide as a thickener, with a mass percentage of 3wt%; epoxy resin as a curing agent, with a mass percentage of 1.5wt%; silicone as a defoaming agent, with a mass percentage of 0.5wt%; pyridine as an acid-base regulator, with a mass percentage of 1wt%.

[0153] The monomer structure of the metal organic framework material ZIF-62 is shown in formula (4).

[0154]

[0155] The preparation methods of the metal organic framework ZIF-62 loaded fluorinated carbon nanotube composite (ZIF-62@F-CNTs), conductive carbon paste (4) and laminated solid aluminum electrolytic capacitor in Example 4 are the same as those in Example 1.

[0156] Example 5

[0157] The difference between Example 5 and Example 1 is that the metal organic framework material ZIF-8 is replaced with ZIF-78 to obtain a metal organic framework ZIF-78 loaded fluorinated carbon nanotube composite (ZIF-78@F-CNTs). Among them, the raw materials of the conductive carbon paste (5) are as follows in terms of mass percentage: ZIF-78@F-CNTs as a conductive material, with a mass percentage of 30wt%; water as a solvent, with a mass percentage of 52wt%; polyetheretherketone as a matrix polymer, with a mass percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a mass percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a mass percentage of 1.5wt%; titanium dioxide as a thickener, with a mass percentage of 3wt%; epoxy resin as a curing agent, with a mass percentage of 1.5wt%; silicone as a defoaming agent, with a mass percentage of 0.5wt%; pyridine as an acid-base regulator, with a mass percentage of 1wt%.

[0158] The monomer structure of the metal organic framework material ZIF-78 is shown in formula (5).

[0159]

[0160] The preparation methods of the metal organic framework ZIF-78 loaded fluorinated carbon nanotube composite (ZIF-78@F-CNTs), conductive carbon paste (5) and laminated solid aluminum electrolytic capacitor in Example 5 are the same as those in Example 1.

[0161] At the same time, the present invention also conducts a comparative test to better illustrate the conductive carbon paste and the laminated solid aluminum electrolytic capacitor of the present invention.

[0162] Comparative Example 1

[0163] In Comparative Example 1, commercially available conductive carbon slurry (6) is used, wherein the conductive material is graphite.

[0164] The preparation method of the laminated solid aluminum electrolytic capacitor in Comparative Example 1 is the same as that in Example 1.

[0165] Comparative Example 2

[0166] The difference between comparative example 2 and example 1 is that fluorinated graphite is used as the conductive material. The components of the conductive carbon paste (7) are as follows in terms of mass percentage: fluorinated graphite as the conductive material, with a mass percentage of 30 wt%; water as the solvent, with a mass percentage of 52 wt%; polyetheretherketone as the matrix polymer, with a mass percentage of 10 wt%; sodium dodecylbenzenesulfonate as the surfactant, with a mass percentage of 0.5 wt%; polyvinylidene fluoride as the binder, with a mass percentage of 1.5 wt%; titanium dioxide as the thickener, with a mass percentage of 3 wt%; epoxy resin as the curing agent, with a mass percentage of 1.5 wt%; silicone as the defoaming agent, with a mass percentage of 0.5 wt%; pyridine as the acid-base regulator, with a mass percentage of 1 wt%.

[0167] The preparation method of the conductive carbon paste (7) and the laminated solid aluminum electrolytic capacitor in Comparative Example 2 is the same as that in Example 1.

[0168] Comparative Example 3

[0169] The difference between Comparative Example 3 and Example 1 is that carbon nanotubes are used as the conductive material. The components of the conductive carbon paste (8) are as follows in terms of mass percentage: carbon nanotubes as the conductive material, with a mass percentage of 30wt%; water as the solvent, with a mass percentage of 52wt%; polyetheretherketone as the matrix polymer, with a mass percentage of 10wt%; sodium dodecylbenzenesulfonate as the surfactant, with a mass percentage of 0.5wt%; polyvinylidene fluoride as the binder, with a mass percentage of 1.5wt%; titanium dioxide as the thickener, with a mass percentage of 3wt%; epoxy resin as the curing agent, with a mass percentage of 1.5wt%; silicone as the defoaming agent, with a mass percentage of 0.5wt%; pyridine as the acid-base regulator, with a mass percentage of 1wt%.

[0170] The preparation method of the conductive carbon paste (8) and the laminated solid aluminum electrolytic capacitor in Comparative Example 3 is the same as that in Example 1.

[0171] Comparative Example 4

[0172] The difference between Comparative Example 4 and Example 1 is that a metal organic framework ZIF-8 loaded carbon nanotube composite (ZIF-8@CNTs) is used as the conductive material, wherein the carbon nanotubes are not fluorinated.

[0173] The components of the conductive carbon paste (9) are calculated by weight percentage as follows: ZIF-8@CNTs as a conductive material, with a weight percentage of 30wt%; water as a solvent, with a weight percentage of 52wt%; polyetheretherketone as a matrix polymer, with a weight percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a weight percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a weight percentage of 1.5wt%; titanium dioxide as a thickener, with a weight percentage of 3wt%; epoxy resin as a curing agent, with a weight percentage of 1.5wt%; silicone as a defoaming agent, with a weight percentage of 0.5wt%; pyridine as an acid-base regulator, with a weight percentage of 1wt%.

[0174] The preparation method of the metal organic framework ZIF-8 loaded carbon nanotube composite (ZIF-8@CNTs), conductive carbon paste (9) and laminated solid aluminum electrolytic capacitor in Comparative Example 4 is the same as that in Example 1.

[0175] Comparative Example 5

[0176] In Comparative Example 5, an acidic MOFs material is used to replace the metal organic framework material ZIF-8 in Example 1 to obtain a MOFs material-loaded fluorinated carbon nanotube composite (MOFs@F-CNTs).

[0177] Preparation of MOFs materials

[0178] Zinc nitrate hexahydrate and terephthalic acid in a molar ratio of 1:1 were added to N,N-dimethylformamide to obtain a 0.1 mol / L metal salt solution and an organic ligand solution. The metal salt solution was slowly added to the organic ligand solution at a rate of 1 mL / min under magnetic stirring, and the mixture was stirred for 20 min to obtain a mixed solution. The mixed solution was transferred to a polytetrafluoroethylene-lined stainless steel autoclave, sealed, and the temperature was controlled at 120°C. The reaction was performed for 24 h, cooled to room temperature, and centrifuged at a speed of 4000 rpm for 10 min to obtain a gray solid. The gray solid was washed 3 times with deionized water, then washed 3 times with methanol, and dried under vacuum at 80°C for 12 h to obtain MOFs material.

[0179] Preparation of MOFs@F-CNTs

[0180] Add 300mL of a mixture of N-methylpyrrolidone and water to a 1000mL stainless steel reactor, start stirring and adjust the speed to 50rpm, add 10g of polyvinylpyrrolidone (PVP-K50) to the mixture, add 30g of fluorinated carbon nanotubes that have been acidified at room temperature with trifluoroacetic anhydride / hydrogen peroxide, and 30g of the MOFs material prepared in the above steps to the reactor in batches, react at room temperature for 1h, then heat to 260℃ and continue to react for 6h, cool naturally to room temperature, and centrifuge to obtain a solid product. The solid product was ultrasonically cleaned with ethanol, then ultrasonically cleaned with pure water, and dried at 80℃ for 8 hours to obtain a MOFs material-loaded fluorinated carbon nanotube composite.

[0181] Preparation of conductive carbon paste (10)

[0182] The components in the conductive carbon paste (10) are calculated by weight as follows: MOFs@F-CNTs as a conductive material, with a weight percentage of 30wt%; water as a solvent, with a weight percentage of 52wt%; polyetheretherketone as a matrix polymer, with a weight percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a weight percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a weight percentage of 1.5wt%; titanium dioxide as a thickener, with a weight percentage of 3wt%; epoxy resin as a curing agent, with a weight percentage of 1.5wt%; silicone as a defoaming agent, with a weight percentage of 0.5wt%; pyridine as an acid-base regulator, with a weight percentage of 1wt%.

[0183] The preparation method of the conductive carbon paste (10) and the laminated solid aluminum electrolytic capacitor in Comparative Example 5 is the same as that in Example 1.

[0184] Comparative Example 6

[0185] The difference between Comparative Example 6 and Example 1 is that a metal organic framework ZIF-8 supported graphite composite (ZIF-8@graphite) is used as the conductive material.

[0186] The components of the conductive carbon paste (11) are as follows in terms of mass percentage: ZIF-8@graphite as a conductive material, with a mass percentage of 30wt%; water as a solvent, with a mass percentage of 52wt%; polyetheretherketone as a matrix polymer, with a mass percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a mass percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a mass percentage of 1.5wt%; titanium dioxide as a thickener, with a mass percentage of 3wt%; epoxy resin as a curing agent, with a mass percentage of 1.5wt%; silicone as a defoaming agent, with a mass percentage of 0.5wt%; pyridine as an acid-base regulator, with a mass percentage of 1wt%.

[0187] The preparation method of the metal organic framework ZIF-8 loaded graphite composite (ZIF-8@graphite), conductive carbon paste (11) and laminated solid aluminum electrolytic capacitor in Comparative Example 6 is the same as that in Example 1.

[0188] Comparative Example 7

[0189] The difference between Comparative Example 7 and Example 1 is that a metal organic framework ZIF-8 loaded graphite fluoride composite (ZIF-8@graphite fluoride) is used as the conductive material.

[0190] The components of the conductive carbon paste (12) are calculated in percentage by mass as follows: ZIF-8@graphite fluoride as a conductive material, with a mass percentage of 30wt%; water as a solvent, with a mass percentage of 52wt%; polyetheretherketone as a matrix polymer, with a mass percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a mass percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a mass percentage of 1.5wt%; titanium dioxide as a thickener, with a mass percentage of 3wt%; epoxy resin as a curing agent, with a mass percentage of 1.5wt%; silicone as a defoaming agent, with a mass percentage of 0.5wt%; pyridine as an acid-base regulator, with a mass percentage of 1wt%.

[0191] The preparation methods of the metal organic framework ZIF-8 loaded graphite fluoride composite (ZIF-8@graphite fluoride), conductive carbon paste (12) and laminated solid aluminum electrolytic capacitor in Comparative Example 7 are the same as those in Example 1.

[0192] Comparative Example 8

[0193] The difference between Comparative Example 8 and Example 1 is that commercially available fluorinated graphene is used as the conductive material.

[0194] The components of the conductive carbon paste (13) are calculated in percentage by mass as follows: fluorinated graphene as a conductive material, with a mass percentage of 30wt%; water as a solvent, with a mass percentage of 52wt%; polyetheretherketone as a matrix polymer, with a mass percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a mass percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a mass percentage of 1.5wt%; titanium dioxide as a thickener, with a mass percentage of 3wt%; epoxy resin as a curing agent, with a mass percentage of 1.5wt%; silicone as a defoaming agent, with a mass percentage of 0.5wt%; pyridine as an acid-base regulator, with a mass percentage of 1wt%.

[0195] The preparation method of the conductive carbon paste (13) and the laminated solid aluminum electrolytic capacitor in Comparative Example 8 is the same as that in Example 1.

[0196] Comparative Example 9

[0197] The difference between Comparative Example 9 and Example 1 is that a metal organic framework ZIF-8 loaded fluorinated graphene composite (ZIF-8@fluorinated graphene) is used as the conductive material.

[0198] The components of the conductive carbon paste (14) are calculated in percentage by mass as follows: ZIF-8@fluorinated graphene as a conductive material, with a mass percentage of 30wt%; water as a solvent, with a mass percentage of 52wt%; polyetheretherketone as a matrix polymer, with a mass percentage of 10wt%; sodium dodecylbenzenesulfonate as a surfactant, with a mass percentage of 0.5wt%; polyvinylidene fluoride as a binder, with a mass percentage of 1.5wt%; titanium dioxide as a thickener, with a mass percentage of 3wt%; epoxy resin as a curing agent, with a mass percentage of 1.5wt%; silicone as a defoaming agent, with a mass percentage of 0.5wt%; pyridine as an acid-base regulator, with a mass percentage of 1wt%.

[0199] The preparation method of the metal organic framework ZIF-8 loaded fluorinated graphene composite (ZIF-8@fluorinated graphene), conductive carbon paste (14) and laminated solid aluminum electrolytic capacitor in Comparative Example 9 is the same as that in Example 1.

[0200] In the present invention, the performance of the conductive materials used in Examples 1 to 5 and Comparative Examples 1 to 9 was tested.

[0201] The test method is as follows:

[0202] Specific surface area

[0203] The measurement principle of the static capacity method is adopted: when using the specific surface area meter for measurement, the sample is placed under high vacuum to adsorb the sample; then, the adsorption volume is measured by the gas-borne method or liquid phase method. According to the adsorption volume, combined with the standard curve of the specific surface area meter, the specific surface area of ​​the material can be measured.

[0204] Water absorption

[0205] Moisture absorption test method: Place the test sample flat in an oven at 50°C, dry for 24 hours, then cool it to room temperature in a dryer, weigh each sample to an accuracy of 1 mg; then place the sample completely in air with a relative humidity of 50%, and measure the mass change of the sample after a certain period of time at the specified temperature.

[0206] The test results are shown in Table 1.

[0207] Table 1 Summary of properties of conductive materials in embodiments and comparative examples

[0208] Group Conductive Materials <![CDATA[Specific surface area (m 2 / g)]]> Water absorption (mg / g) Example 1 ZIF-8@F-CNTs 530.6 10.2 Example 2 ZIF-67@F-CNTs 632.1 11.5 Example 3 ZIF-14@F-CNTs 581.5 12.1 Example 4 ZIF-62@F-CNTs 598.6 11.8 Example 5 ZIF-78@F-CNTs 660.3 9.6 Comparative Example 1 graphite 19.6 51.3 Comparative Example 2 Graphite Fluoride 15.8 31.6 Comparative Example 3 Carbon Nanotubes 540.5 78.5 Comparative Example 4 ZIF-8@CNTs 574.6 72.1 Comparative Example 5 MOFs@F-CNTs 520.7 89.6 Comparative Example 6 ZIF-8@Graphite 560.8 76.4 Comparative Example 7 ZIF-8@Graphite Fluoride 574.6 92.3 Comparative Example 8 Fluorinated graphene 570.8 86.2 Comparative Example 9 ZIF-8@Fluorinated Graphene 552.8 85.4

[0209] It can be seen from Table 1 that the water absorption rate of the conductive material in the embodiment of the present invention is lower, and the moisture absorption rate of the electrode material of the stacked capacitor is relatively small (less than 12.1 mg / g). When used as a raw material of the conductive carbon slurry for the stacked solid capacitor, it can prevent water from penetrating into the cathode conductive polymer layer, avoiding the decomposition and failure of the conductive polymer, thereby ensuring that the stacked capacitor has a lower impedance and loss. (Specific surface area greater than 500m 2 / g, water absorption rate is less than 15mg / g, these two parameters must be met at the same time to be qualified.)

[0210] Meanwhile, the conductive carbon pastes used in Examples 1 to 5 and Comparative Examples 1 to 9 were subjected to performance tests in the present invention.

[0211] Test standard: solid content 30% to 50%, viscosity 1±0.2dPa·s, curing temperature 110℃ to 125℃, curing time 15min to 35min, square resistance ≤10Ω. See Table 2 for test results.

[0212] Table 2 Test conditions and sheet resistance of conductive carbon paste in the embodiments and comparative examples

[0213] Group Conductive Materials Solid content (wt%) Viscosity (dPa·s) Curing conditions Square resistance Example 1 ZIF-8@F-CNTs 48 1.15 115℃×25min 6.5Ω Example 2 ZIF-67@F-CNTs 48 1.15 115℃×25min 7.2Ω Example 3 ZIF-14@F-CNTs 48 1.15 115℃×25min 8.3Ω Example 4 ZIF-62@F-CNTs 48 1.15 115℃×25min 8.1Ω Example 5 ZIF-78@F-CNTs 48 1.15 115℃×25min 5.6Ω Comparative Example 1 graphite 48 1.15 115℃×25min 11.5Ω Comparative Example 2 Graphite Fluoride 48 1.15 115℃×25min 12.3Ω Comparative Example 3 Carbon Nanotubes 48 1.15 115℃×25min 10.8Ω Comparative Example 4 ZIF-8@CNTs 48 1.15 115℃×25min 13.5Ω Comparative Example 5 MOFs@F-CNTs 48 1.15 115℃×25min 14.9Ω Comparative Example 6 ZIF-8@Graphite 48 1.15 115℃×25min 15.2Ω Comparative Example 7 ZIF-8@Graphite Fluoride 48 1.15 115℃×25min 13.9Ω Comparative Example 8 Fluorinated graphene 48 1.15 115℃×25min 14.6Ω Comparative Example 9 ZIF-8@Fluorinated Graphene 48 1.15 115℃×25min 15.6Ω

[0214] The present invention adopts a metal organic framework loaded fluorinated carbon nanotube composite as the conductive material of the conductive carbon paste, so that the conductivity of the conductive carbon paste is significantly improved compared with graphite, and the impedance is reduced and the loss is reduced.

[0215] At the same time, the performance of the laminated solid aluminum electrolytic capacitors prepared in Examples 1 to 5 and Comparative Examples 1 to 9 was tested.

[0216] Capacitor double 85 test:

[0217] The so-called double 85 test is to place the capacitor in an environment with a temperature of 85°C and a humidity of 85% for a period of time, and then test whether the performance of the capacitor meets the standards.

[0218] The pass standard of the loss tangent (tanδ) test is: ≦0.06 (120Hz / +20℃).

[0219] Equivalent series resistance (ESR) test pass standard: ≦20mΩ (100kHz / +20℃).

[0220] Leakage current test pass standard: I≦0.1CV(μA) [test voltage 2V / 2 minutes, capacitor capacity C is 621μF, and the measured leakage current exceeds 124μA, which is unqualified].

[0221] In the present invention, the laminated solid aluminum electrolytic capacitors prepared in Examples 1 to 5 and Comparative Examples 1 to 9 were subjected to double 85% tests, and the moisture absorption time was 168 hours. The test results are shown in Table 3.

[0222] Table 3 Test results of laminated solid aluminum electrolytic capacitors in the embodiments and comparative examples

[0223] project Loss tangent (tanδ) ESR(mΩ) Leakage current (μA) Whether it has passed the double 85 test Example 1 0.0143 4.9 22.6 yes Example 2 0.0178 5.2 28.4 yes Example 3 0.0212 5.2 31.3 yes Example 4 0.0183 4.3 21.4 yes Example 5 0.0197 5.8 24.5 yes Comparative Example 1 0.08243 21.7 152.3 no Comparative Example 2 0.10354 23.9 161.2 no Comparative Example 3 0.09728 22.7 155.4 no Comparative Example 4 0.09136 25.1 187.9 no Comparative Example 5 0.07125 27.3 176.1 no Comparative Example 6 0.08326 28.3 190.6 no Comparative Example 7 0.08923 29.1 184.3 no Comparative Example 8 0.09561 27.9 180.5 no Comparative Example 9 0.07236 25.8 168.2 no

[0224] The conductive carbon paste of the present invention is applied to the transition layer of the laminated solid aluminum electrolytic capacitor, so that the waterproof performance of the laminated capacitor is significantly improved. The laminated capacitor can pass the double 85% test, and the comprehensive performance is improved and the service life is extended.

[0225] It should be understood that the terms used herein are only for the purpose of describing specific example embodiments and are not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms "one", "an" and "said" as used herein may also be meant to include plural forms. The terms "include", "comprise", "contain", and "have" are inclusive, and therefore specify the existence of stated features, steps, operations, elements and / or parts, but do not exclude the existence or addition of one or more other features, steps, operations, elements, parts, and / or combinations thereof. The method steps, processes, and operations described herein are not interpreted as necessarily requiring them to be performed in the specific order described or illustrated, unless the execution order is clearly indicated. It should also be understood that additional or alternative steps may be used.

[0226] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A conductive carbon paste, characterized in that: The raw material of the conductive carbon paste includes a fluorine-containing conductive material, and the fluorine-containing conductive material is a metal organic framework-loaded fluorinated carbon nanotube composite.

2. The conductive carbon paste according to claim 1, characterized in that: The mass percentage of the fluorine-containing conductive material in the raw materials of the conductive carbon paste is 30wt% to 50wt%; The total weight percentage of each raw material is 100 wt%.

3. The conductive carbon paste according to claim 1, characterized in that: The metal organic framework-supported fluorinated carbon nanotube composite is prepared from a metal organic framework material, fluorinated carbon nanotubes, a binder and a second solvent; Among them, the mass percentage of each component is: Metal organic framework materials: 20wt% to 40wt%; Fluorinated carbon nanotubes: 20wt% to 40wt%; Binder: 10wt% to 30wt%; Second solvent: balance; The mass percentages of the various components add up to 100 wt%.

4. The conductive carbon paste according to claim 3, characterized in that: The metal organic framework material in the metal organic framework-loaded fluorinated carbon nanotube composite includes ZIF-1, ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-11, ZIF-12, ZIF-14, ZIF-20, ZIF-21, ZIF-22, ZIF-23, ZIF-60, ZIF-61 , one or more combinations of ZIF-62, ZIF-64, ZIF-65, ZIF-67, ZIF-68, ZIF-69, ZIF-70, ZIF-73, ZIF-74, ZIF-75, ZIF-76, ZIF-77, ZIF-78, ZIF-79, ZIF-82, ZIF-90, ZIF-91, and ZIF-92; wherein ZIF is a zeolite imidazolate framework structure material.

5. The conductive carbon paste according to any one of claims 1 to 4, characterized in that: The raw materials of the conductive carbon paste also include at least one of a matrix polymer, a binder, a thickener, and a curing agent; Preferably, in the conductive carbon paste, by mass percentage, the mass percentage of the base polymer is 8wt% to 13wt%, the mass percentage of the binder is 0.5wt% to 1.5wt%, the mass percentage of the thickener is 1.5wt% to 3.0wt%, and the mass percentage of the curing agent is 1.5wt% to 2.5wt%.

6. The conductive carbon paste according to any one of claims 1 to 5, characterized in that: The raw materials of the conductive carbon slurry also include at least one of a surfactant, a defoaming agent, an acid-base regulator, and a first solvent; Preferably, in the conductive carbon paste, in terms of mass percentage, the mass percentage of the surfactant is 0.5wt% to 1.5wt%, the mass percentage of the defoaming agent is 0.5wt% to 1.0wt%, the mass percentage of the acid-base regulator is 0.5wt% to 1.0wt%, and the mass percentage of the first solvent is 40wt% to 60wt%.

7. A method for preparing the conductive carbon paste according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: Mixing the raw materials of the conductive carbon paste and stirring and dispersing them to obtain a dispersion; The dispersion is sequentially ground, filtered, pH adjusted and centrifuged to obtain the conductive carbon slurry; Preferably, the pH is adjusted to 7-9; the average particle size of the filtrate obtained after filtration is preferably 40 μm-60 μm.

8. A method for preparing a multilayer capacitor, characterized in that: The method comprises coating the conductive carbon paste described in any one of claims 1 to 6 or the conductive carbon paste prepared by the preparation method described in claim 7 on the cathode region of the chemically formed foil before preparing the lead-out layer to form a transition layer of the stacked capacitor.

9. The method for preparing a multilayer capacitor according to claim 8, wherein: The conductive carbon paste is coated on the cathode area of ​​the formed foil by dipping, blade coating or screen printing; Preferably, the conductive carbon paste has a viscosity of 1±0.2 dPa·s and a solid content of 30% to 50%.

10. A multilayer capacitor, characterized in that: The transition layer of the stacked capacitor comprises the conductive carbon paste according to any one of claims 1 to 6 or the conductive carbon paste prepared by the preparation method according to claim 7; Or, the multilayer capacitor is made by the preparation method described in any one of claims 8-9.

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