CN113178334A - High specific volume, low resistance, ultra-thin type negative electrode foil and solid-state aluminum electrolytic capacitor - Google Patents

High specific volume, low resistance, ultra-thin type negative electrode foil and solid-state aluminum electrolytic capacitor Download PDF

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CN113178334A
CN113178334A CN202110473612.2A CN202110473612A CN113178334A CN 113178334 A CN113178334 A CN 113178334A CN 202110473612 A CN202110473612 A CN 202110473612A CN 113178334 A CN113178334 A CN 113178334A
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negative electrode
electrode foil
specific volume
aluminum substrate
resin
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CN113178334B (en
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吕上
朱金勇
蒋武斌
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Anhui Nanuo Foil Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/20—Acidic compositions for etching aluminium or alloys thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0032—Processes of manufacture formation of the dielectric layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/07—Dielectric layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors

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Abstract

The invention relates to a high-specific-volume low-resistance ultrathin negative electrode foil and a solid aluminum electrolytic capacitor, wherein the negative electrode foil comprises an aluminum base material and a dielectric layer, holes are formed in the surface of the aluminum base material through etching, the dielectric layer is a coating rolled on the holes and the surface of the aluminum base material, slurry of the coating is oxide dielectric particles of valve metal, metal particles, organic resin, a dispersing agent and a solvent according to the mass ratio of 1: 0.05-0.2: 0.1-1: 0.0001-0.01: 5-50, the average particle size of the oxide dielectric particles of the valve metal is 10-500 nm, and the average particle size of the metal particles is 5-100 nm. On one hand, the specific volume is improved on the premise of enhancing the adhesion between the dielectric layer and the aluminum base material layer, and meanwhile, the dielectric layer contains metal particles to enhance the conductivity of the negative electrode foil; on the other hand, the coating has the advantages of reduced resistance, small thickness, strong adhesiveness and safety.

Description

High specific volume, low resistance, ultra-thin type negative electrode foil and solid-state aluminum electrolytic capacitor
The application relates to a production process of a negative electrode foil with the application date of 2019, 03 and 20, the application number of 201910214877.3 and divisional applications of the negative electrode foil and a polymer solid-state aluminum electrolytic capacitor.
Technical Field
The invention belongs to the technical field of capacitors, and particularly relates to a high-specific-volume, low-resistance and ultrathin negative electrode foil, and a solid aluminum electrolytic capacitor manufactured by using the negative electrode foil.
Background
As is well known, miniaturization of electronic components has been an industry hotspot. In recent years, various smart terminals have been rapidly developed in the fields of consumer electronics for consumer use, industrial manufacturing, automotive electronics, military communications, and the like. The realization of these terminal functions is free from component support without miniaturization, and the realization of more functions in a limited space has become a necessary trend, and the demand for component miniaturization will continue to continue.
The capacitor is an essential device in an electronic circuit as a basic component, is generally used for functions of AC resistance direct current, filtering, bypass, coupling and quick charge and discharge, can be used for reducing ripples and absorbing noise generated by a switching regulator, and can also be used for post-stage voltage stabilization to improve the stability and transient response capability of equipment. No ripple noise or residual jitter should appear in the power supply output. Among various types of capacitors, the solid-state aluminum electrolytic capacitor is still the most cost-effective choice in terms of volume-to-volume ratio and volume-to-price ratio, and is widely applied to consumer electronics, communication products, automation control, automobile industry, photoelectric products, high-speed railways, aviation and military equipment, and the like.
According to the capacitance calculation formula C = epsilon S/d of the capacitor, wherein C is the capacitance, epsilon is the dielectric constant of the dielectric, S is the facing area of the positive electrode plate and the negative electrode plate of the capacitor, and d is the distance between the positive electrode plate and the negative electrode plate, it can be seen that the capacitance of the capacitor is in direct proportion to the dielectric constant of the dielectric, the area of the electrode plates is in direct proportion, and the distance between the electrodes is in inverse proportion.
In the actual structure of the liquid aluminum electrolytic capacitor, there are two capacitors, in which the positive electrode foil and the electrolyte form a capacitor C1, the electrolyte and the negative electrode foil form a capacitor C2, and the two capacitors are connected in series, and the total capacity C = (C1 × C2)/(C1 + C2), and in order to increase the total capacity, the capacities of the positive electrode foil and the negative electrode foil need to be increased. The first method of capacity increase is to increase the dielectric constant of the dielectric, using a valve metal with a high oxide dielectric constant, such as: tantalum, niobium, and the like, but these metals are rare metals, and are relatively small in the amount of resources on the earth, expensive, and lower in cost performance than aluminum; the second method is to reduce the distance between electrodes, and in the solid aluminum electrolytic capacitor, the dielectric is Al oxide203The film layer, the distance between electrodes is the thickness of the oxide film, and the positive electrode foil film layer is in direct proportion to the capacitor withstand voltage, so that the thickness of the oxide film cannot be reduced at the same level as the withstand voltage. The oxide film of the negative foil is stable, and the extremely thin oxide layer formed on the surface of the negative foil is only slightly thicker than the natural oxide film and cannot be reduced any more; the third method is a conventional method for increasing the area of the electrode foil to increase the capacity and miniaturize the capacity. For a long time, the miniaturization of solid aluminum electrolytic capacitors relies on the surface-enlarging corrosion technology of aluminum foil, i.e., the surface of the aluminum foil is corroded into spongy cavities by an electrochemical corrosion method, so that the area of the cavities is enlarged. With the continuous progress of the technology, the face expansion times are increased year by year. However, the current technology has reached its physical limit basically, the increasing speed is very slow, taking the negative electrode foil as an example, the specific volume is 500uF/cm2The left and right are already at the maximumHowever, after the capacitor is connected with the positive foil capacitor in series, the whole capacitance capacity is still greatly influenced, and the further miniaturization of the solid-state aluminum electrolytic capacitor is prevented.
Research has been conducted for many years to increase the specific volume of the negative foil and reduce the loss of the capacity of the positive foil, and a more advanced scheme is to attach a material with a high dielectric constant to an aluminum substrate and increase epsilon to increase the capacity. Among them, Japanese capacitor corporation developed a method of plating titanium on an aluminum substrate by vapor deposition, the titanium surface was in the form of a pyramid having irregularities to increase the surface area to some extent, and then passivated to form TiO on the surface2Film due to TiO2Has a specific Al content203The specific volume of the negative electrode foil made by the method is greatly improved, but the specific volume can only reach 1000 uF/cm due to the nonideal surface area2To the extent that, in low voltage bulk capacitors, there is still some loss of positive foil capacitance.
However, in order to increase the capacitance of a capacitor, chinese patent 201080013193.4 relates to an electrode structure, a capacitor, a battery, and a method for manufacturing an electrode structure, the electrode structure having: aluminum material; a dielectric layer formed on a surface of the aluminum material; and an intermediate layer containing aluminum and carbon, which is formed between the aluminum material and the dielectric layer and in at least a partial region of the surface of the aluminum material, wherein the dielectric layer contains dielectric particles containing a valve metal, and an organic layer is formed on at least a partial surface of the dielectric particles. Meanwhile, the manufacturing method of the electrode structure body comprises the following steps: 1) a mixture layer forming step of forming a mixture layer containing dielectric particles of a valve metal and a binder on a surface of an aluminum material; 2) and a heating step of heating the aluminum material having the mixture layer formed thereon in a state of being placed in a space containing a hydrocarbon-containing substance.
Although the electrode structure described above has a dielectric particle layer of valve metal attached to an aluminum foil to increase the specific volume of the electrode, the dielectric particles are tightly bonded to the aluminum foil through aluminum carbide, and therefore, heating is required in a space containing a hydrocarbon substance, which is not preferable in terms of safety and economy.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an improved high-specific-volume low-resistance ultrathin negative electrode foil.
Meanwhile, the invention also relates to a solid-state aluminum electrolytic capacitor made of the negative electrode foil, metal particles are added into dielectric particles of valve metal, the resistance of a covering layer is reduced, the ESR of the capacitor is small, and meanwhile, in a product with the same capacity, the volume of the product is obviously reduced, and great contribution is made to the miniaturization of the capacitor.
In order to solve the technical problems, the invention adopts a technical scheme that:
a high specific volume, low resistance and ultra-thin type negative electrode foil comprises an aluminum substrate and a dielectric layer, wherein holes are formed on the surface of the aluminum substrate by etching, the aperture of each hole is 50-500 nm, and the depth of each hole is 100-1000 nm; the dielectric layer is a coating rolled on the holes and the surface of the aluminum substrate, and the thickness of the coating formed on the surface of the aluminum substrate after rolling is 50% -80% of the thickness of the coating formed on the surface of the aluminum substrate before rolling, wherein the slurry of the coating is selected from dielectric oxide particles of valve metal, metal particles, organic resin, dispersing agent and solvent according to the mass ratio of 1: 0.05-0.2: 0.1-1: 0.0001-0.01: 5-50, the average particle size of the dielectric oxide particles of the valve metal is 10-500 nm, and the average particle size of the metal particles is 5-100 nm.
Preferably, the slurry is coated on the surface of the aluminum substrate with holes, dried for 10-300 s in a high temperature furnace at 100-300 ℃, and then carbonized at 400-600 ℃ in the absence of oxygen to form a pre-rolling coating, wherein the absence of oxygen refers to an inert gas atmosphere, a vacuum atmosphere or a reducing atmosphere.
Preferably, the pores are distributed over the surface of the aluminum substrate at a density of 1X 103～9×105Per cm2。
Preferably, the aperture of the hole is 100-300 nm; the hole depth of the hole is 400-700 nm; hole(s)The holes are distributed on the surface of the aluminum substrate at a density of 1X 104～5×104Per cm2. At this time, dense bonding of the dielectric layer and the surface of the aluminum substrate can be optimally achieved.
Preferably, the thickness of the coating formed on the surface of the aluminum substrate after rolling is 0.5 to 5 μm.
According to a specific embodiment and preferred aspect of the present invention, the oxide dielectric particles of the valve metal have an average particle diameter of 10 to 500nm, and the valve metal is one or more of magnesium, thorium, cadmium, tungsten, tin, tantalum, titanium, hafnium, zirconium and niobium. Generally, the average particle size of the oxide dielectric particles of the selected valve metal is 40 to 200 nm. In the case of non-spherical particles, the particle size is defined as the average of the major axis diameter and the minor axis diameter.
Preferably, the metal particles have an average particle diameter of 5 to 100nm and are one or more of silver, gold, nickel, copper, titanium, cobalt, zirconium and chromium.
Then, with respect to the above-mentioned particles, the shape thereof is not limited, and a sphere, a flake, a column, or the like is common.
Meanwhile, the organic resin in the present application is: a carboxyl-modified polyolefin resin; a vinyl acetate resin; vinyl chloride resin; vinyl chloride-vinyl acetate copolymer resin; a vinyl alcohol resin; a fluorinated vinyl resin; acrylic resin; a polyester resin; a urethane resin; an epoxy resin; urea resin; a phenolic resin; an acrylonitrile resin; nitrocellulose resins; paraffin wax; synthetic resins such as polyethylene wax; and natural resins such as wax, tar, glue, lacquer, rosin, beeswax and the like, and the main functions of the coating are as follows: 1. enabling physical connection between the dielectric particles; 2. after the heat treatment, the dielectric particles are carbonized to form electrical continuity between the dielectric particles and the aluminum substrate.
The solvents in this application are: ketones, esters, alcohols, aromatics, aliphatics, water, etc., which mainly function as: 1. the viscosity of the slurry is adjusted, so that the coating is convenient; 2. and after drying, volatilizing to leave a gap, so that the electrolyte can conveniently enter the coating and contact with the dielectric particles.
The dispersing agent in this example is: fatty acids, fatty amides, metallic soaps and the like, which mainly play a role in: reduce the aggregation of particles in a dispersion system and facilitate the mixing and dispersion of slurry.
The other technical scheme of the invention is as follows: the solid-state aluminum electrolytic capacitor comprises a core package, and particularly, the core package comprises the high-specific-volume and ultrathin negative electrode foil.
Meanwhile, the production process of the high specific volume and ultrathin negative electrode foil comprises the following steps:
s1, selecting an aluminum substrate, wherein the aluminum content is 99.0-99.9%;
s2, a step of forming a dielectric layer, comprising the steps of: a) preparing slurry, namely selecting dielectric oxide particles of valve metal, metal particles, organic resin, a dispersant and a solvent according to the mass ratio of 1: 0.05-0.2: 0.1-1: 0.0001-0.01: 5-50, mixing, stirring and uniformly mixing; b) etching the surface of the aluminum substrate to form holes, coating the slurry on the surface of the aluminum substrate with the holes, drying the surface, feeding the aluminum substrate into a rolling mill, pressing the coating into the holes, and compacting the coating on the holes and the surface of the aluminum substrate; c) carbonizing, wherein the aperture of the hole is 50-500 nm, and the hole depth is 100-1000 nm; and the thickness of the coating formed on the surface of the aluminum substrate after rolling is 50-80% of the thickness of the coating formed on the surface of the aluminum substrate before rolling.
Preferably, the selected aluminum substrate is put into a hydrochloric acid solution with the concentration of 0.1-4 mol/L and the temperature of 20-100 ℃ for soaking for 5-60 s, then a nitric acid solution with the concentration of 2-4 wt% is adopted for washing, and then the aluminum substrate is washed by clean water and dried. The method mainly comprises the steps that an aluminum substrate is soaked in an acid solution, impurities in the aluminum substrate and aluminum form a micro-battery effect, holes are corroded in the surface of the aluminum substrate, and meanwhile, the size of the expected holes is achieved by controlling the reaction temperature, the acid concentration and the reaction time, so that the finally formed dielectric layer and the aluminum substrate are high in combination firmness and not prone to falling off.
Preferably, before the step c), drying for 10-300 s in a high temperature furnace at 100-300 ℃ to complete the drying of the coating surface. The purpose of the drying at this point is: part of the solvent in the mixture layer is volatilized, the corresponding volume is emptied, and surface drying is realized.
Preferably, in step c) of S2, the heat treatment temperature is 400 to 600 ℃, the heat treatment time is 1 to 48 hours, and the carbonization is performed under the condition of isolating oxygen.
The conditions for excluding oxygen mainly refer to an inert gas atmosphere, a vacuum atmosphere or a reducing atmosphere.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
on one hand, the specific volume is improved on the premise of enhancing the adhesion between the dielectric layer and the aluminum base material layer, and meanwhile, the dielectric layer contains metal particles to enhance the conductivity of the negative electrode foil; on the other hand, the coating has the advantages of reduced resistance, small thickness, strong adhesiveness and safety.
Drawings
Fig. 1 is a schematic structural view of a negative electrode foil according to the present invention before rolling;
fig. 2 is a schematic view of a rolled negative electrode foil according to the present invention;
FIG. 3 is a schematic view of the particle structure of FIG. 1 (before rolling);
FIG. 4 is a schematic view of the particle structure of FIG. 2 (after rolling);
wherein: 1. an aluminum substrate; 10. a hole; 2. a dielectric layer; 2a, a bonding layer; 2b, a cover layer; c. oxide dielectric particles of a valve metal; d. metal particles.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
Referring to fig. 1 and 2, the present embodiment provides a high specific volume, low resistance, ultra-thin negative electrode foil, which includes an aluminum substrate 1 and a dielectric layer 2 formed on the surface of the aluminum substrate 1.
Specifically, the production process of the high specific volume, low resistance and ultrathin negative electrode foil comprises the following steps:
s1, selecting an aluminum substrate, wherein the aluminum substrate is an aluminum foil with the aluminum content of 99.5% and the thickness of 30 mu m;
s2, a step of forming a dielectric layer, comprising the steps of: a) preparing slurry; b) etching the surface of the aluminum substrate to form holes, coating the slurry on the surface of the aluminum substrate with the holes, drying the surface, feeding the aluminum substrate into a rolling mill, pressing the coating into the holes, and compacting the coating on the holes and the surface of the aluminum substrate; c) and carbonizing.
In the step a), the oxide dielectric particles of the valve metal, the metal particles, the organic resin, the dispersant and the solvent are mixed in a mass ratio of 1: 0.15: mixing the materials at a ratio of 0.6: 0.0002: 7, stirring and mixing uniformly to prepare slurry.
In this example, the oxide of the valve metal is titanium dioxide particles, and the average particle diameter of the titanium dioxide particles is 50 to 80 nm; the metal particles are silver particles of 30-60 nm; the adopted organic resin is phenolic resin; the solvent used is acetone; the adopted dispersant is triolein.
Step b) it can be carried out in three steps: firstly, forming holes; secondly, coating to form a coating; and thirdly, rolling, and elaborating each step in detail below.
Soaking the selected aluminum substrate in 0.5mol/L hydrochloric acid solution at the temperature of 60 +/-2 ℃ for 10s, washing by using 3wt% nitric acid aqueous solution, washing by using clean water and drying. Through the aluminum base material soaking in the acid solution, impurities in the aluminum base material and aluminum form a micro-battery effect, holes are corroded on the surface of the aluminum base material, and meanwhile, the size of the expected holes is achieved by controlling the reaction temperature, the acid concentration and the reaction time, so that the finally formed dielectric layer and the aluminum base material are high in combination firmness and not prone to falling off
Specifically, the holes 10 are recessed from the surface of the aluminum substrate 1, the diameter of the holes 10 is 100-150 nm, the depth of the holes is 400-500 nm, and the distribution density of the holes on the surface of the aluminum substrate 1 is 3 × 103Per cm2。
Secondly, the prepared slurry is directly and uniformly coated on the surface of the aluminum substrate, and then dried in a tunnel furnace at 200 + -5 ℃ for 90 seconds to dry the surface of the coating, wherein the thickness of the coating formed upward from the surface of the aluminum substrate (excluding the wall surface of the hole) is 4.2 μm.
In (c), a part of the coating is pressed into the holes and fills the holes to form a bonding layer 2a by rolling, and the remaining part is pressed against the bonding layer 2a and the surface covering layer 2b of the aluminum substrate 1.
In this example, the thickness of the covering layer 2b after rolling was 2.6 μm, i.e. 61.9% of the thickness of the coating layer before rolling.
In step c), the rolled foil is put into a reducing atmosphere for heat treatment at 580 +/-5 ℃ for 12 +/-1 h, so that the organic resin in the coating is carbonized to form a conductive framework, and the titanium dioxide nano-particles and the silver particles are attached to the surface of the aluminum substrate and are electrically conducted with the aluminum substrate 1 to form the dielectric layer 2.
Meanwhile, as shown in fig. 3 and 4, the formation processes of the bonding layer and the capping layer before and after the rolling can be clearly expressed, and the approximate distribution of the titanium dioxide particles and the silver particles can also be seen.
The specific volume of the aluminum substrate after etching is 25uF/cm through testing2(ii) a The specific volume of the negative electrode foil with the dielectric layer formed thereon was 4897. mu.F/cm2(10 times the specific volume in the prior art, and thus can be referred to as a high specific volume negative foil); intercepting a negative foil sample with the length multiplied by the width of 15cm multiplied by 1cm, and carrying out resistance detection along the length direction, wherein the resistance of the negative foil sample is 13.2m omega; the adhesion obtained by tape stripping was 92%, and the calculation method for the adhesion test was: adhesion (%) = (weight of sample after peeling-weight of aluminum foil itself used as a base material ÷ (weight of sample before peeling-weight of aluminum foil itself used as a base material) × 100%, which is a means commonly used in the art and will not be described in detail herein, and specific volume after adhesion test is 4521. mu.F/cm2。
Meanwhile, the voltage of the electrode foil is selected to be 11VF and the specific volume is selected to be 220 muF/cm2The size of the positive electrode foil is 0.6cm × 4cm (length × width), and then the negative electrode foil in the present example is selected, the size of the negative electrode foil is 0.6cm × 5cm (length × width),making into solid aluminum electrolytic capacitors, and then randomly taking out 10 capacitor products from the solid aluminum electrolytic capacitors in the same batch for testing, wherein the average value of the capacitance of the capacitor is 407 muF; the average value of ESR was 4.9 m.OMEGA.; after a life test in which a rated voltage was impressed at 105 ℃ for 3000 hours, the average value of the capacity of the capacitor was 397. mu.F, the rate of change in the capacity was-2.46%, and the average value of ESR was 5.4 m.OMEGA..
Example 2
The structure and the process of the high specific volume, low resistance and ultrathin negative electrode foil related to the implementation are basically the same as those of the embodiment 1, and the difference is that:
1) the forming process of the holes in this example is: soaking the selected aluminum substrate in a hydrochloric acid solution with the concentration of 0.5mol/L and the temperature of 80 ℃ for 15s, then washing the aluminum substrate by using a 3wt% nitric acid aqueous solution, then washing the aluminum substrate by using clear water and drying the aluminum substrate.
Specifically, the aperture of the holes 10 is 150 to 250nm, the depth of the holes is 450 to 550nm, and the distribution density of the holes on the surface of the aluminum substrate 1 is 1 × 104Per cm2。
2) In this example, titanium dioxide particles, silver particles, an organic resin, a dispersant, and a solvent are mixed in a mass ratio of 1: 0.10: mixing the materials at a ratio of 0.6: 0.0002: 8, stirring and mixing uniformly to prepare slurry.
3) In this example, the slurry coating is applied to the surface of the aluminum substrate, dried for 50 seconds in a tunnel furnace at 280 + -5 deg.C to dry the surface of the coating, and then rolled.
4) And in the step c), the rolled foil is put into an inert gas atmosphere for heat treatment, the temperature of the heat treatment is 500 +/-5 ℃, the time of the heat treatment is 20 +/-1 h, so that the organic resin in the coating is carbonized to form a conductive framework, and the titanium dioxide nano-scale particles and the silver particles are attached to the surface of the aluminum substrate and are electrically conducted with the aluminum substrate to form the dielectric layer 2.
The specific volume of the aluminum substrate after etching is 53 mu F/cm2(ii) a The specific volume of the negative electrode foil with the dielectric layer formed thereon was 4832. mu.F/cm2(ii) a The resistance of a negative foil sample with a length of 15cm × 1cm was measured along the length direction, and the resistance was 13.9m omega; adhesion obtained by tape stripping was 97%; the specific volume after the adhesion test was 4711. mu.F/cm2。
Meanwhile, the voltage of the electrode foil is also selected to be 11VF and the specific volume is selected to be 220 muF/cm2The size of the positive electrode foil is 0.6cm multiplied by 4cm, then the negative electrode foil in the embodiment is selected, the size of the negative electrode foil is 0.6cm multiplied by 5cm, the solid-state aluminum electrolytic capacitor is manufactured, then 10 capacitor products are arbitrarily taken out from the solid-state aluminum electrolytic capacitors in the same batch for testing, and the average value of the capacitance of the capacitor is 408 uF; the average value of ESR was 5.0 m.OMEGA.; after a life test in which a rated voltage was impressed at 105 ℃ for 3000 hours, the capacity became 399. mu.F on average, the rate of change in capacity was-2.21%, and the average value of ESR was 5.7 m.OMEGA..
Example 3
The structure and the process of the high specific volume, low resistance and ultrathin negative electrode foil related to the implementation are basically the same as those of the embodiment 1, and the difference is that:
1) the forming process of the holes in this example is: soaking the selected aluminum substrate in a hydrochloric acid solution with the concentration of 1mol/L and the temperature of 80 ℃ for 20s, then washing by using a 3wt% nitric acid aqueous solution, then washing by using clear water and drying.
Specifically, the aperture of the holes 10 is 250-300 nm, the depth of the holes is 600-700 nm, and the distribution density of the holes on the surface of the aluminum substrate 1 is 4 × 105Per cm2。
2) In this example, titanium dioxide particles, silver particles, an organic resin, a dispersant, and a solvent are mixed in a mass ratio of 1: 0.2: mixing the materials at a ratio of 0.6: 0.0002: 8, stirring and mixing uniformly to prepare slurry.
3) In this example, the slurry coating applied to the surface of the aluminum substrate was dried in a tunnel oven at 110. + -. 5 ℃ for 240 seconds to effect surface drying of the coating and then rolled, and the thickness of the covering layer 2b after rolling was 2.7 μm, i.e., 64.3% of the thickness of the coating before rolling.
4) And in the step c), the rolled foil is put into a vacuum atmosphere for heat treatment, the temperature of the heat treatment is 450 +/-5 ℃, the time of the heat treatment is 30 +/-1 h, so that the organic resin in the coating is carbonized to form a conductive framework, and the titanium dioxide nano-scale particles and the silver particles are attached to the surface of the aluminum substrate and are electrically conducted with the aluminum substrate to form the dielectric layer 2.
The specific volume of the aluminum substrate after etching is 97 mu F/cm2(ii) a The specific volume of the negative electrode foil with the dielectric layer formed thereon was 4175. mu.F/cm2(ii) a Intercepting a negative foil sample with the length multiplied by the width of 15cm multiplied by 1cm, and carrying out resistance detection along the length direction, wherein the resistance of the negative foil sample is 14.8m omega; adhesion obtained by tape stripping was 99%; specific volume after adhesion test was 4123. mu.F/cm2。
Meanwhile, the voltage of the electrode foil is also selected to be 11VF and the specific volume is selected to be 220 muF/cm2The size of the positive electrode foil is 0.6cm multiplied by 4cm, then the negative electrode foil in the embodiment is selected, the size of the negative electrode foil is 0.6cm multiplied by 5cm, the solid-state aluminum electrolytic capacitor is made, then 10 capacitor products are arbitrarily taken out from the solid-state aluminum electrolytic capacitors in the same batch for testing, and the average value of the capacitance of the capacitor is 405 muF; the average value of ESR was 5.2 m.OMEGA.; after a life test in which a rated voltage was impressed at 105 ℃ for 3000 hours, the capacity became 394. mu.F on average, the capacity change rate was-2.72%, and the average value of ESR was 5.9 m.OMEGA..
Comparative example 1
The negative foil structure and process involved in this comparative example are essentially the same as example 1, except that:
1) according to the comparative example, titanium dioxide particles, organic resin, a dispersing agent and a solvent are mixed according to the mass ratio of 1: 0.5: 0.001: 8, and are stirred and mixed uniformly to prepare slurry.
2) In the comparative example, the foil on which the coating was formed was directly fed into a heating furnace without being subjected to a rolling process to be carbonized.
The specific volume of the aluminum substrate after etching is 53 mu F/cm2(ii) a The specific volume of the negative electrode foil formed with the dielectric layer was 5811. mu.F/cm2(ii) a Intercepting a negative foil sample with the length multiplied by the width of 15cm multiplied by 1cm, and carrying out resistance detection along the length direction, wherein the resistance of the negative foil sample is 14.2m omega; adhesion obtained by tape stripping was 44%; specific volume after adhesion test was 2549. mu.F/cm2。
At the same time, the electrode foil is also selectedThe pressure is 11VF and the specific volume is 220 muF/cm2The size of the positive electrode foil is 0.6cm multiplied by 4cm, then the negative electrode foil in the comparative example is selected, the size of the negative electrode foil is 0.6cm multiplied by 5cm, the solid-state aluminum electrolytic capacitor is made, then 10 capacitor products are arbitrarily taken out from the solid-state aluminum electrolytic capacitors in the same batch for testing, and the average value of the capacitance of the capacitor is 408 muF; the average value of ESR was 7.7 m.OMEGA.; after a life test in which a rated voltage was impressed at 105 ℃ for 3000 hours, the average value of the capacity was 308. mu.F, the rate of change in the capacity was-24.51%, and the average value of ESR was 18.7 m.OMEGA..
Comparative example 2
The negative foil structure and process involved in this comparative example are essentially the same as example 1, except that:
1) the formation process of the holes in this comparative example was: soaking the selected aluminum substrate in a hydrochloric acid solution with the concentration of 1.5mol/L and the temperature of 90 ℃ for 25s, then washing by using a 3wt% nitric acid aqueous solution, then washing by using clear water and drying.
Specifically, the diameter of the holes 10 is 600 to 700nm, the depth of the holes is 1100 to 1200nm, and the distribution density of the holes on the surface of the aluminum substrate 1 is 2 × 106Per cm2。
2) According to the comparative example, titanium dioxide particles, organic resin, a dispersing agent and a solvent are mixed according to the mass ratio of 1: 0.5: 0.001: 8, and are stirred and mixed uniformly to prepare slurry.
3) In this comparative example, the thickness of the covering layer 2b after rolling was 1.9 μm, that is, 45.2% of the thickness of the coating layer before rolling.
The specific volume of the aluminum substrate after etching is 204 mu F/cm after testing2(ii) a The specific volume of the negative electrode foil with the dielectric layer formed thereon was 3148. mu.F/cm2(ii) a Intercepting a negative foil sample with the length multiplied by the width of 15cm multiplied by 1cm, and carrying out resistance detection along the length direction, wherein the resistance of the negative foil sample is 17.8m omega; adhesion obtained by tape stripping was 99%; specific volume after adhesion test was 3127. mu.F/cm2。
Meanwhile, the voltage of the electrode foil is also selected to be 11VF and the specific volume is selected to be 220 muF/cm2The size of the positive electrode foil is 0.6cm x 4cm, and the negative electrode foil in the present embodiment is selectedThe size of the negative electrode foil is 0.6cm multiplied by 5cm, the negative electrode foil is made into a solid-state aluminum electrolytic capacitor, then 10 capacitor products are randomly taken out from the solid-state aluminum electrolytic capacitors in the same batch for testing, and the average value of the capacity of the capacitor is 405 muF; the average value of ESR was 8.1 m.OMEGA.; after a life test in which a rated voltage was impressed at 105 ℃ for 3000 hours, the capacity became 398. mu.F on average, the capacity change rate was-1.73%, and the average value of ESR was 9.0 m.OMEGA..
Comparative example 3
The negative foil structure and process involved in this comparative example are essentially the same as example 1, except that:
1) in this comparative example, the surface of the aluminum substrate was etched (i.e., the surface was flat and had no holes).
2) According to the comparative example, titanium dioxide particles, organic resin, a dispersing agent and a solvent are mixed according to the mass ratio of 1: 0.5: 0.001: 8, and are stirred and mixed uniformly to prepare slurry.
3) The thickness of the cover layer after rolling was 3.5 μm, i.e. 83.3% of the thickness of the coating layer before rolling.
The specific volume of the aluminum substrate which is not subjected to the etching treatment is tested to be 63uF/cm2(ii) a The specific volume of the negative electrode foil with the dielectric layer formed thereon was 5538. mu.F/cm2(ii) a Intercepting a negative foil sample with the length multiplied by the width of 15cm multiplied by 1cm, and carrying out resistance detection along the length direction, wherein the resistance of the negative foil sample is 13.1m omega; adhesion obtained by tape stripping was 11%; the specific volume after the adhesion test was 735. mu.F/cm2。
Meanwhile, the voltage of the electrode foil is also selected to be 11VF and the specific volume is selected to be 220 muF/cm2The size of the positive electrode foil is 0.6cm multiplied by 4cm, then the negative electrode foil in the embodiment is selected, the size of the negative electrode foil is 0.6cm multiplied by 5cm, the solid-state aluminum electrolytic capacitor is made, then 10 capacitor products are arbitrarily taken out from the solid-state aluminum electrolytic capacitors in the same batch for testing, and the average value of the capacitance of the capacitor is 403 muF; the average value of ESR was 7.2 m.OMEGA.; after a life test in which a rated voltage was impressed at 105 ℃ for 3000 hours, the capacity became 136. mu.F on average, the capacity change rate was-66.25%, and the average value of ESR was 45.1 m.OMEGA..
As can be seen from the comparative analysis, the main factors affecting the specific volume, adhesion and the like of the negative electrode foil are shown in two aspects: firstly, etching to form a hole; and II, rolling. Meanwhile, there is a close relationship between the two, such as:
the dielectric layer formed by shallow etching or no etching, rolling and carbonization can fall off and have insufficient adhesion in a tape stripping test; the holes formed by etching are too large or too deep, and a large amount of dielectric layers are sunk into the aluminum substrate after rolling, so that although the adhesion meets the requirement, the titanium dioxide particles, the silver particles and the aluminum foil embedded in the aluminum substrate are tightly combined, therefore, the titanium dioxide particles and the silver particles embedded in the aluminum foil cannot play the role of a dielectric medium, and the specific volume is greatly reduced.
In addition, in the solid-state aluminum electrolytic capacitors produced by using the negative electrode foils according to examples 1 to 3, the capacity of the capacitor is increased and the resistance of the coating is reduced by selecting titanium dioxide particles having an extremely high dielectric constant as valve metal particles and combining silver particles, and then the ESR of the capacitor is significantly improved and the capacity change of the capacitor is small, particularly, the service life is long, and in addition, the miniaturization and the current resistance of the solid-state aluminum electrolytic capacitor are contributed.
Finally, it should be noted that: although the present invention has been described in detail with reference to the embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (10)

1. A high specific volume, low resistance, ultra-thin type negative electrode foil, which includes aluminum substrate and dielectric layer, its characterized in that: etching the surface of the aluminum substrate to form holes, wherein the hole diameter is 50-500 nm, and the hole depth is 100-1000 nm; the dielectric layer is a coating rolled on the surfaces of the holes and the aluminum substrate, and the thickness of the coating formed on the surface of the aluminum substrate after rolling is 50% -80% of the thickness of the coating formed on the surface of the aluminum substrate before rolling, wherein the slurry of the coating is prepared from dielectric oxide particles of valve metal, metal particles, organic resin, dispersing agent and solvent according to the mass ratio of 1: 0.05-0.2: 0.1-1: 0.0001-0.01: 5-50, the average particle size of the dielectric oxide particles of the valve metal is 10-500 nm, and the average particle size of the metal particles is 5-100 nm.
2. The high specific volume, low resistance, ultra-thin type negative electrode foil according to claim 1, wherein: coating the slurry on the surface of the aluminum substrate with the holes, drying the aluminum substrate in a high-temperature furnace at 100-300 ℃ for 10-300 s, and then carbonizing the aluminum substrate at 400-600 ℃ in the absence of oxygen to form a pre-rolling coating, wherein the absence of oxygen refers to an inert gas atmosphere, a vacuum atmosphere or a reducing atmosphere.
3. The high specific volume, low resistance, ultra-thin type negative electrode foil according to claim 1, wherein: the holes are distributed on the surface of the aluminum substrate at a density of 1 × 103～9×105Per cm2。
4. The high specific volume, low resistance, ultra-thin type negative electrode foil according to claim 1, wherein: the aperture of the hole is 100-300 nm; the hole depth of the hole is 400-700 nm.
5. The high specific volume, low resistance, ultra-thin type negative foil of claim 1: the valve metal is one or more of magnesium, thorium, cadmium, tungsten, tin, tantalum, titanium, hafnium, zirconium and niobium; the metal particles are one or more of silver, gold, nickel, copper, titanium, cobalt, zirconium and chromium.
6. The high specific volume, low resistance, ultra-thin type negative electrode foil according to claim 1, wherein: the thickness of the coating formed on the surface of the aluminum substrate after rolling is 0.5 to 5 μm.
7. The high specific volume, ultra-thin type negative electrode foil according to claim 1, wherein: the grease is as follows: a carboxyl-modified polyolefin resin; a vinyl acetate resin; vinyl chloride resin; vinyl chloride-vinyl acetate copolymer resin; a vinyl alcohol resin; a fluorinated vinyl resin; acrylic resin; a polyester resin; a urethane resin; an epoxy resin; urea resin; a phenolic resin; an acrylonitrile resin; nitrocellulose resins; paraffin wax; synthetic resins such as polyethylene wax; and natural resins such as wax, tar, glue, lacquer or rosin.
8. The high specific volume, ultra-thin type negative electrode foil according to claim 1, wherein: the solvent is as follows: ketones, esters, alcohols, aromatics, aliphatics or water.
9. The high specific volume, ultra-thin type negative electrode foil according to claim 1, wherein: the dispersant is as follows: fatty acids, fatty amides or metallic soaps.
10. A solid-state aluminum electrolytic capacitor comprises a core package, and is characterized in that: the core package comprises the high specific volume, ultra-thin body negative foil of any one of claims 1-9.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020080558A1 (en) * 1998-01-23 2002-06-27 Seiji Nonaka Electrode metal material, capacitor and battery formed of the material and method of producing the material and the capacitor and battery
CN102426924A (en) * 2011-10-13 2012-04-25 李荐 High-performance aluminum/carbon composite electrode foil and preparation method thereof
CN102832392A (en) * 2012-06-27 2012-12-19 长沙业翔能源科技有限公司 Current collector carbon coated aluminum foil and its preparation method
CN105469989A (en) * 2016-01-21 2016-04-06 珠海华冠电容器有限公司 Fabrication method of high-temperature resistant chip aluminum electrolytic capacitor
CN107316745A (en) * 2017-07-18 2017-11-03 丰宾电子（深圳）有限公司 Electrode structural body and aluminium electrolutic capacitor for aluminium electrolutic capacitor
CN107354498A (en) * 2017-07-18 2017-11-17 丰宾电子（深圳）有限公司 A kind of manufacture method of the electrode foil for aluminum electrolytic capacitors of high pressure high power capacity

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101677101B1 (en) * 2009-03-23 2016-11-17 도요 알루미늄 가부시키가이샤 Electrode structure, capacitor, battery, and method for producing electrode structure
CN103825008B (en) * 2014-03-21 2016-01-13 中国科学院新疆理化技术研究所 A kind of preparation method of three-dimensional porous positive plate of lithium battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020080558A1 (en) * 1998-01-23 2002-06-27 Seiji Nonaka Electrode metal material, capacitor and battery formed of the material and method of producing the material and the capacitor and battery
CN102426924A (en) * 2011-10-13 2012-04-25 李荐 High-performance aluminum/carbon composite electrode foil and preparation method thereof
CN102832392A (en) * 2012-06-27 2012-12-19 长沙业翔能源科技有限公司 Current collector carbon coated aluminum foil and its preparation method
CN105469989A (en) * 2016-01-21 2016-04-06 珠海华冠电容器有限公司 Fabrication method of high-temperature resistant chip aluminum electrolytic capacitor
CN107316745A (en) * 2017-07-18 2017-11-03 丰宾电子（深圳）有限公司 Electrode structural body and aluminium electrolutic capacitor for aluminium electrolutic capacitor
CN107354498A (en) * 2017-07-18 2017-11-17 丰宾电子（深圳）有限公司 A kind of manufacture method of the electrode foil for aluminum electrolytic capacitors of high pressure high power capacity

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