CN112151276B - Electrode foil, method for producing same, and electrolytic capacitor - Google Patents
Electrode foil, method for producing same, and electrolytic capacitor Download PDFInfo
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- CN112151276B CN112151276B CN202010970544.6A CN202010970544A CN112151276B CN 112151276 B CN112151276 B CN 112151276B CN 202010970544 A CN202010970544 A CN 202010970544A CN 112151276 B CN112151276 B CN 112151276B
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- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The application provides an electrode foil, which comprises an aluminum foil substrate and a titanium-containing coating metallurgically combined on at least one surface of the aluminum foil substrate, wherein the titanium-containing coating is composed of titanium oxide and a carbon material, and at least part of the titanium oxide is a strip-shaped oxide with the length-diameter ratio not less than 5. The coating of the present application is metallurgically bonded to the aluminum foil substrate using titanium oxide directly, which can achieve much higher capacity than can be achieved by the prior art. The stability of the titanium oxide is greatly improved by compounding the titanium oxide with the carbon material, and the problem that the titanium oxide is singly used in the electrode and has a short plate with poor stability is solved. And partial titanium oxide is mutually wound to form a woven structure by selecting the strip shape, so that the cohesive force of the coating can be improved, single particles and fibers in the coating are prevented from falling off, the density of the coating is improved, the liquid erosion resistance of the coating is improved, and the service life of an electrode material is prolonged. The application also claims a manufacturing method of the electrode foil and an electrolytic capacitor based on the electrode foil.
Description
Technical Field
The present invention relates to the field of electrode foil materials and manufacturing technology, and more particularly to an electrode foil, a manufacturing method thereof, and an electrolytic capacitor using the same.
Background
The electrolytic capacitor is a capacitor having a valve metal surface oxide film as a dielectric layer, and the electrode material is a valve metal. The 'valve metal' is a metal which has a natural oxide film in air and can be obtained into a controllable oxide film through anodic oxidation, and the core characteristic of the 'valve metal' as the material of the electrolytic capacitor is that the 'self-healing' characteristic is realized, namely, the defects of the oxide film (natural or generated by anodic oxidation) on the surface of the valve metal can be automatically repaired under the conditions of electrolyte (or solid electrolyte) and applied voltage without causing further breakdown. The valve metals currently used for electrolytic capacitors mainly include aluminum, tantalum, niobium and titanium, and each of these valve metals has excellent properties.
The valve metal of the aluminum electrolytic capacitor is aluminum, the electrode foil is aluminum foil, the oxide film on the surface of the aluminum foil is used as a dielectric layer, and the capacitance formula is C ═ epsilon S/(4k pi d), wherein epsilon is the dielectric constant of the dielectric layer (aluminum oxide), S is the specific surface area of the aluminum foil, and d is the thickness of the dielectric layer (aluminum oxide). In order to obtain larger capacity, the aluminum foil of the electrode generally adopts an etching method to increase the specific surface area. However, the capacity of the traditional corrosion method obtained by the material reduction method is limited, the current technical development approaches to the ceiling, and on the other hand, the acid-base pollution is heavy and the environment protection situation is severe.
In order to increase the capacity of the electrode aluminum foil, many practitioners use a method of adding a substance with a higher dielectric constant to increase the epsilon value, and titanium and its oxides and salts (such as titanate) become three main directions of addition.
The capacity of the electrolytic capacitor can be improved by using titanium as the valve metal because the dielectric constant of the oxide is higher than that of aluminum, the capacity is actually improved by adding the titanium element, namely, an oxide film inevitably existing on the surface of the titanium element (titanium is automatically generated after being exposed in air), and the titanium oxide has the defect of instability as shown in many documents and patents.
Therefore, how to develop and improve the above-mentioned shortcomings of the prior art is the objective of the related industry, and the present application is proposed by the designer of the present application based on the idea of creation and design with years of experience, through many studies and trials of sample tests, and many modifications and improvements.
Disclosure of Invention
The invention provides an electrode foil, a manufacturing method thereof and an electrolytic capacitor using the same, aiming at the problems of the electrode foil and the electrolytic capacitor.
In one aspect, the invention provides an electrode foil, which comprises an aluminum foil substrate and a titanium-containing coating metallurgically bonded on at least one surface of the aluminum foil substrate, wherein the titanium-containing coating is composed of titanium oxide and a carbon material, and at least part of the titanium oxide is strip-shaped oxide with the length-diameter ratio not less than 5.
In some embodiments, the titanium-containing coating has a single-sided thickness of 50 to 5000 nm.
In some embodiments, the elongated oxide having an aspect ratio of not less than 5 has a diameter of 5 to 500nm and a length of 26nm to 50 μm.
In some embodiments, the elongated oxide is a solid fiber.
In other embodiments, the elongated oxide is a hollow nanotube, preferably a nanotube.
In some embodiments, at least one of an in situ generated aluminum carbide or oxycarbide is present between the aluminum foil substrate and the titanium-containing coating.
In some embodiments, not less than 2 wt% of the oxide of titanium is a long-strip oxide having an aspect ratio of not less than 5.
In some embodiments, the oxide of titanium further comprises a particulate oxide having an aspect ratio of less than 3.
In some embodiments, the particulate oxide has a cumulative 90% particle size (D90) value of 5 to 100 times the cumulative 10% particle size (D10), more preferably in the interval 10 to 70 times, as measured by laser diffraction scattering particle size distribution.
In some embodiments, the particulate oxide has a cumulative 50% particle size (D50) in the range of 5 nm to 1000nm as determined by laser diffraction scattering particle size distribution.
In some embodiments, the titanium-containing coating layer comprises at least one of in situ generated titanium carbide or oxycarbide.
In some embodiments, the carbon material in the titanium-containing coating layer is at least partially in the form of elongated strips having an aspect ratio of not less than 10, which are distributed in the titanium-containing coating layer as a network of self-woven structures.
In some embodiments, the carbon material is at least partially in the form of one or more of a particulate, flake.
In some embodiments, the material type of the carbon material is one or more of carbon black, graphite, carbon nanotubes, graphene, activated carbon, pyrolytic carbon, carbon fibers, and glassy carbon.
In some embodiments, the titanium-containing coating has a grooved texture that integrally segments the titanium-containing coating into discontinuous coatings.
In another aspect, the present invention provides an electrolytic capacitor using the electrode foil as at least one of a positive electrode and a negative electrode.
In still another aspect, the present invention provides a method of manufacturing an electrode foil, including:
preparing a titanium-containing coating, forming a prefabricated coating of a titanium-containing mixture on at least one side of an aluminum foil substrate, and sintering the aluminum foil substrate with the prefabricated coating in an oxygen-isolated atmosphere to obtain the titanium-containing coating consisting of titanium oxide and a carbon material, wherein the titanium-containing mixture comprises a titanium-containing compound and a carbon source, and part of the titanium-containing compound is in a strip shape with the length-diameter ratio of not less than 5: and (5) preparing a product.
In some embodiments, the titanium-containing compound is selected from an oxide of titanium, a hydroxide of titanium, an organic polymer of titanium, a halide of titanium, or mixtures thereof.
In some embodiments, the carbon source is at least one of a carbon material, an organic polymeric carbon source, a hydrocarbon carbon source.
In some embodiments, in the case that the carbon source is a carbon material, the material type of the carbon material is one or more of carbon black, graphite, carbon nanotubes, graphene, activated carbon, pyrolytic carbon, carbon fibers, and glassy carbon, and the form of the carbon material is at least partially in the form of a long strip with an aspect ratio of not less than 10.
In some embodiments, not less than 2 wt% of the titanium oxide is an elongated oxide having an aspect ratio of not less than 5, in some embodiments the elongated oxide is a solid fiber, in other embodiments a hollow nanotube, preferably a nanotube.
In some embodiments, the oxide of titanium further comprises a particulate oxide having an aspect ratio of less than 3.
In some embodiments, the particulate oxide preferably has a cumulative 90% particle size (D90) value of 5 to 100 times the cumulative 10% particle size (D10), more preferably in the interval 10 to 70 times, as measured by laser diffraction scattering particle size distribution.
In some embodiments, the atmosphere to exclude oxygen in the step of forming the titanium-containing coating layer is a reducing atmosphere, preferably at least one of a hydrocarbon atmosphere, a carbon atmosphere, a hydrogen atmosphere, a water gas atmosphere, and a CO atmosphere.
In some embodiments, the sintering in the step of forming the titanium-containing coating layer is at least one of heating sintering, laser sintering, electric spark sintering, electromagnetic induction sintering, spark plasma sintering, high pressure sintering, and pulsed light sintering.
In some embodiments, the step of forming the titanium-containing coating layer is performed by heating and sintering, wherein the sintering temperature is 300 to 640 ℃, and the heating and sintering time is 10min to 200 h.
In some embodiments, the step of forming the titanium-containing coating layer comprises subjecting the titanium-containing mixture and a solvent to a high-energy activation step in a container, wherein the high-energy activation step is at least one of high-pressure fluid jet milling, hammer milling, bar milling, ball milling, sand milling and high-speed shearing, and the high-energy activation step expands and energizes the strip shape in the mixture to form a net-shaped expanded self-interwoven structural embryo shape in the titanium-containing slurry.
In some embodiments, the titanium-containing compound further comprises titanium-containing compound particles with an aspect ratio of less than 3, wherein the titanium-containing compound particles are activated and uniformly dispersed in the elongated network self-interlacing structure; the titanium-containing mixture with the strip-shaped net-shaped self-interweaving structure forms a coating on the surface of the aluminum foil substrate by means of coating, spraying, printing or hot pressing, and a special coating structure with a net-shaped self-interweaving structure in an overall (partially contained in some embodiments) strip-shaped form can be formed after a solvent is removed. After the diligent research of the inventor, the requirement of forming the reticular self-woven structure meets the requirement of a proper length-diameter ratio, the length-diameter ratio is at least more than 5, and more preferably more than or equal to 10. Under the condition of the same length-diameter ratio, the hollow nano-tube-shaped titanium-containing oxide is more favorable for forming a net-shaped self-woven structure than the solid fiber, and is a more preferable scheme.
In some embodiments, in the step of forming the titanium-containing coating, a groove pattern is formed to divide the titanium-containing coating into discontinuous coatings, and the groove pattern can release stress to prevent cracking of the coating, improve liquid permeation efficiency of the coating, and improve bending resistance of the electrode foil.
In another aspect, the present invention provides an electrode foil that is a product obtained by the above-mentioned method for manufacturing an electrode foil.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a photomicrograph of the coating morphology of one aspect (example 2) of an electrode foil provided by the present invention; is a photographed picture obtained by magnifying the surface of the electrode foil to 5 ten thousand times with a scanning electron microscope.
Fig. 2 is a microphotograph of a coating morphology of one aspect (example 4) of the electrode foil provided by the present invention, which is a photographed picture of a surface of the electrode foil magnified to 5 ten thousand times by using a scanning electron microscope.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
In the present invention, the term "metallurgical bond" refers to a deep bond formed by interdiffusion of atoms between the interfaces of two parts composed of different components and in-situ formation of a separate phase component containing the two parts.
In the present invention, the "carbon material" may be any carbon material, and examples of the preferred carbon material in the present invention include carbon black such as acetylene black, furnace black, and channel black, natural or synthetic graphite, carbon nanotube, graphene, activated carbon, pyrolytic carbon, and glassy carbon, one or two or more of these carbon materials may be used, and a carbon-containing precursor, that is, pyrolytic carbon produced by carbonizing a carbon source may be used.
In the present invention, the "aspect ratio" means L/D, wherein L is the dimension in the length direction of the fiber and D is the fineness, i.e., the diameter.
In the present invention, "in situ generation" means the in situ generation of one or more reinforcing phases (e.g., TiO) in a matrix by chemical reaction under certain conditions2、Al4C4TiC, etc.) as opposed to the concept of directly adding the substance.
In the present invention, "oxide of titanium" means a compound composed of Ti and O, and more commonly includes TiO, TiO2And Ti2O3。
In the present invention, "carbide" refers to a binary compound of carbon and an element (other than hydrogen) having a smaller or similar electronegativity.
In the present invention, "carbon oxide" refers to a carbon-oxygen-containing multi-component compound obtained by reacting carbon with a metal oxide.
In the present invention, "wt%" means weight percentage.
In the present invention, "D10" means a particle size having a cumulative bai distribution of 10%, i.e., the volume content of particles smaller than this particle size is 10% of the total particles.
In the present invention, "D50" means a particle size distribution of 50% in cumulative particle size, also called median or median, which is a typical value representing the size of the particle size, which accurately divides the population into two equal parts, i.e. 50% of the particles exceed this value and 50% of the particles fall below this value.
In the present invention, "D90" means a particle size having a cumulative particle distribution of 90%, i.e., the volume content of particles smaller than this particle size is 90% of the total particles. Others may be analogized.
In the present invention, "hydroxide of titanium" means a compound formed by titanium and hydroxyl group, and includes tetravalent titanium hydroxide, and divalent and trivalent titanium hydroxides
In the present invention, the term "organic polymer of titanium" refers to an organometallic polymer having a main chain containing Ti-O bonds and pendant organic groups.
In the present invention, the term "titanium halide" means that titanium and halogen are easily volatilized to form a high-valent titanium halide, and that divalent and trivalent titanium halides are also formed.
In the present invention, the "organic polymer carbon source" refers to organic substances containing carbon, such as saccharides, fatty acids, petroleum, natural resins, artificial resins, and artificial polymers containing at least oxyhydrocarbon, which are naturally occurring and are characterized in that they are decomposed and carbonized at a predetermined temperature to produce pyrolytic carbon.
In the present invention, "reducing atmosphere" means various reducing gases and gas mixtures, and the reducing gases are mainly hydrocarbon atmosphere, carbon atmosphere, hydrogen atmosphere, water gas atmosphere, and CO atmosphere.
In the present invention, "coating" refers to a method of applying a paste polymer, a molten polymer or a polymer melt to a film through a certain quantitative pattern of coating heads to obtain a composite material (film).
In the present invention, "spray coating" refers to a coating method in which spray coating is applied to the surface of an object to be coated by dispersing into uniform and fine droplets by means of pressure or centrifugal force by means of a spray gun or a disc atomizer.
In the present invention, "printing" means transferring a polymer paste, a polymer melt or a polymer melt to the surface of a film by a process such as pressing.
In the present invention, "hot pressing" refers to a process of forming a coating layer on the surface of a film by extruding or pressing a substance while forming a paste-like polymer, a molten polymer or a polymer melt by heating.
The application provides an electrode foil, including the aluminium foil base member and metallurgical combination in the titanium-containing coating of the at least one side of aluminium foil base member, the titanium-containing coating comprises the oxide and the carbon material of titanium, the oxide at least part of titanium is the rectangular form oxide that length-diameter ratio is not less than 5.
The traditional titanium used as valve metal can improve the capacity of the electrolytic capacitor because the dielectric constant of the oxide is higher than that of aluminum, and the scheme of adding titanium element actually improves the capacity and is also the inevitable oxide film on the surface of the titanium element.
The coating of the present application is metallurgically bonded to the aluminum foil substrate using titanium oxide directly, which allows much higher capacities than can be achieved in the prior art. However, many documents and patents have described that titanium oxide has a weak point of instability, and the present application has found that the stability of titanium oxide can be improved by compounding titanium oxide having insufficient stability with a carbon material having high stability and coating the carbon material with the carbon material through a large number of experiments, and therefore, the titanium-containing coating layer in the present application is composed of titanium oxide and carbon material. In order to further prevent the titanium coating from easily falling off, creative labor is required to be carried out by technical personnel in the field, part of titanium oxide is strip-shaped oxide with the length-diameter ratio not less than 5, and the strip-shaped oxide can be mutually wound to form a woven structure, so that the cohesive force of the coating can be improved, single particles and fibers in the coating are prevented from falling off, the density of the coating is improved, the liquid corrosion resistance of the coating is improved, and the service life of an electrode material is prolonged.
In various embodiments of the electrode foil of the present application, the titanium-containing coating layer has a single-sided thickness of 50 to 5000nm, a long oxide having an aspect ratio of not less than 5, a diameter of 5 to 500nm, a length of 26nm to 50 μm, and a solid fibrous or hollow tubular state.
Further, in various embodiments of the electrode foil provided herein, there is at least one of aluminum carbide or carbon oxide generated in-situ between the aluminum foil substrate and the titanium-containing coating. The in-situ generation of the compounds by carbon and aluminum can enable the coating to be deeply metallurgically bonded with an aluminum matrix, and the adhesion and the electric conductivity of the coating are improved.
In various embodiments of the electrode foil of the present application, not less than 2 wt% of the oxide of titanium is a long-strip-shaped oxide having an aspect ratio of not less than 5.
On the other hand, the titanium oxide also includes a particulate oxide having an aspect ratio of less than 3.
Through long-term research, the inventor finds that the existence of the granular oxide can control the internal stacking porosity through the particle size and the shape of the granular oxide on one hand, and can improve the total surface area through increasing the coating thickness on the other hand, comprehensively obtain a controllable super-large specific surface area, thereby improving the capacity of the electrode foil.
In various embodiments of the electrode foil, the titanium oxide may be a strip oxide with a length-diameter ratio of not less than 5, so that the highest coating cohesion and compactness can be obtained, and the titanium oxide is more preferable in application scenes requiring high coating adhesion and higher liquid erosion resistance; the titanium oxide can also be a combination of long-strip and granular oxides with a network-like self-woven structure, and is more preferable in application scenarios where the wettability of electrolyte and working liquid needs to be improved and the electrode capacity needs to be higher (closely related to the surface area of the coating).
And further preferably, the particulate oxide has a cumulative 90% particle diameter (D90) value measured by laser diffraction scattering particle size distribution measurement of 5 to 100 times, more preferably in an interval of 10 times to 70 times, the cumulative 10% particle diameter (D10).
What needs to be achieved by creative work of technicians in the field is that a reasonable parameter collocation interval in compounding of large and small particles can effectively utilize space under the condition of the same coating thickness, can effectively improve the specific surface area of the coating and obtain higher capacity, and the reasonable collocation can also enable the small particles to be positioned in gaps of the large particles, can improve the adhesive force and stability of the small particles in the coating and solve the defect that the small particles need more binder phases compared with large particles with the same quality.
Further, the titanium-containing coating layer contains in-situ generated titanium carbide and oxycarbide based on various embodiments of the electrode foil provided herein. The existence of the titanium compound of the carbon can form metallurgical grade combination between the oxide layer of the titanium and the carbon material coated on the surface of the titanium, and the adhesive property and the stability of the oxide of the titanium in the coating are improved.
Based on the various embodiments of the electrode foil provided by the present application, further, the titanium-containing coating layer has grooved lines, which integrally divide the titanium-containing coating layer into discontinuous coating layers.
In another aspect, the present application is also directed to a method for manufacturing a deprotected electrode foil, comprising:
preparing a titanium-containing coating, forming a prefabricated coating of a titanium-containing mixture on at least one side of an aluminum foil substrate, and sintering the aluminum foil substrate with the prefabricated coating in an oxygen-isolated atmosphere to obtain the titanium-containing coating consisting of titanium oxide and a carbon material, wherein the titanium-containing mixture comprises a titanium-containing compound and a carbon source, and part of the titanium-containing compound is in a strip shape with the length-diameter ratio not less than 5; and (5) preparing a product.
The prepared product is as follows: the aluminum foil comprises an aluminum foil substrate and a titanium-containing coating metallurgically combined on at least one surface of the aluminum foil substrate, wherein the titanium-containing coating comprises titanium oxide and a carbon material, and at least part of the titanium oxide is a strip-shaped oxide with the length-diameter ratio not less than 5.
In a further embodiment of the present application, the titanium-containing compound is selected from titanium oxide, titanium hydroxide, organic polymer of titanium, halide of titanium, or a mixture thereof, and the carbon source is an organic polymer carbon source.
The precursor of titanium oxide is prepared by sintering titanium-containing compound, wherein the titanium-containing compound comprises titanium oxide, TiO x(X ranges from about 1 to 2), common ones are for example: TiO, TiO 22And Ti2O3(ii) a Hydroxides of titanium, Ti (OH)x(X ranges from about 2 to 4), common ones are: ti (OH)4(ii) a Organic polymers of titanium, the main chain of which contains Ti — O bonds and the side groups of which are organic radicals, such as: isopropyl tristearate, tetra-n-butyl titanate, isopropyl tris (dioctylphosphonato) titanate, isopropyl triolato titanate, isopropyl tris (dodecylbenzenesulfonyl) titanate, isopropyl tris (dioctylphosphonato) titanate, bis (dioctyloxypyrophosphate) ethylene titanate, tetraisopropyl bis (dioctylphosphato) titanate, diisopropyl bis (acetylacetonate) titanate, diisopropyl bis (ethylacetoacetate) titanate, diisopropyl bis (triethanolamine) titanate, tetra-n-propyl titanate, tetraisopropyl titanate, polybutyl titanate, bis (acetylacetonate) (isobutoxy isopropoxy) titanate, isopropyl bis (acetylacetonate) (ethoxy) titanate, diisobutyl bis (ethylacetoacetate) titanate; of titaniumHalides, titanium and halogens form volatile high-valence titanium halides, and also divalent and trivalent titanium halides, such as: TiCl (titanium dioxide) 4、TiCl3、 TiCl2、TiBr4、TiI4。
The oxide precursor of titanium preferably comprises an organometallic polymer of titanium which during sintering produces an in situ formed oxide of titanium and a cracked carbon coated thereon in situ.
The precursor of the carbon material, i.e. the carbon source, is preferably at least one of organic polymer carbon sources, and the organic polymer carbon source is preferably an aromatic polymer, specifically including benzene hydrocarbon or mono benzene arene, a compound having one benzene ring and derivatives thereof, such as: benzene, phenol, halogenated benzene, toluene, etc.; or polycyclic aromatic hydrocarbons, polycyclic hydrocarbons having a benzene ring or heterocyclic ring common to the ring sides, such as: naphthalene, anthracene,
Flowers, benzopyrene, and the like; or polycyclic compounds in which two or more benzene rings and a heterocyclic ring share a ring edge, which are called fused benzene heterocyclic compounds, such as indole, quinoline, fluorene, and the like.
More preferably, the organic resin is at least one selected from the group consisting of vinyl chloride-vinyl acetate copolymer resin, urea resin, urethane resin, epoxy resin, furan resin, phenol resin, polytetrafluoroethylene, polyvinylidene fluoride, polyamide-vinyl acetate resin, polyvinyl butyral, urethane resin, acrylic resin, vinyl ester resin, vinyl chloride copolymer resin, acrylonitrile resin, polyvinyl pyrrolidone, polyvinyl alcohol, polyamide wax, polyethylene glycol, polyelectrolyte, and vinyl acetate.
The precursor of the carbon material, i.e., the carbon source, is also preferably a hydrocarbon carbon source, and is further preferably a macromolecular hydrocarbon which is solid at ordinary temperature, such as paraffin.
The precursor carbon source of the carbon material is more preferably a mixture of the different carbon sources.
In various embodiments of the electrode foil manufacturing method of the present application, not less than 2 wt% of the titanium oxide in the coating layer after sintering is a long-strip-shaped oxide having an aspect ratio of not less than 5.
On the other hand, the titanium oxide in the sintered coating layer also includes a particulate oxide having an aspect ratio of less than 3.
And further preferably, the particle-shaped oxide in the coating layer after sintering has a cumulative 90% particle diameter (D90) value 5 to 100 times the cumulative 10% particle diameter (D10) as measured by laser diffraction scattering particle size distribution measurement.
In various embodiments of the electrode foil manufacturing method of the present application, the atmosphere for isolating oxygen in the step of forming the titanium-containing coating layer is a reducing atmosphere. The reducing atmosphere is preferably at least one of a hydrocarbon atmosphere, a carbon atmosphere, a hydrogen atmosphere, a water gas atmosphere, and a CO atmosphere. The reducing atmosphere may also include a mixture of the above atmosphere with an inert gas such as N2Ar or He, etc. The atmosphere may also be provided with a vaporizable titanium compound, such as a titanium halide, using a reducing or inert gas as a carrier gas.
In various embodiments of the electrode foil manufacturing method of the present application, the sintering manner in the step of manufacturing the titanium-containing coating layer is at least one of heating sintering, laser sintering, electric spark sintering, electromagnetic induction sintering, spark plasma sintering, high-pressure sintering, and pulsed light sintering.
And further preferably, the step of manufacturing the titanium-containing coating adopts a heating sintering mode, and the sintering temperature is 300-640 ℃. The heating sintering time is different from 10min to 200h, the reaction rate difference is extremely large at different temperatures, the temperature is increased, and the time required by sintering is obviously reduced. The sintering time of other modes is also different, the time range is wide under the influence of the sintering mode and the sintering condition, the time span can be from 0.1 second to 200 hours, particularly, the sintering of laser, electric spark and discharge plasma can be completed within 0.1 second under the condition of the parameter with larger energy, and the longest time is 200 hours under the condition with lower energy.
In various embodiments of the method for manufacturing an electrode foil of the present application, in the step of forming a titanium-containing coating layer, the method for forming a pre-coating layer includes: and mixing the titanium-containing mixture with a solvent to prepare slurry, and forming a coating on the surface of the aluminum foil substrate by coating, spraying, printing or hot pressing the slurry.
In various embodiments of the electrode foil manufacturing method of the present application, in the step of manufacturing the titanium-containing coating layer, a groove pattern is formed to integrally divide the titanium-containing coating layer into discontinuous coating layers. On the one hand, stress can be released, cracks generated by stress which is generated by thermal expansion and cold contraction of the coating in the heating process and cannot be released are relieved, and on the other hand, the specific surface area of the groove lines can be increased, so that the electrode foil obtains larger capacity, and the soaking efficiency of working liquid is improved.
Examples of the invention are provided below:
the electrode foil comprises an aluminum foil substrate and a titanium-containing coating which is metallurgically combined with at least one surface of the aluminum foil substrate, wherein the titanium-containing coating is composed of titanium oxide and a carbon material, and at least part of the titanium oxide is a strip-shaped oxide with the length-diameter ratio not less than 5.
A method of manufacturing an electrode foil, comprising:
preparing a titanium-containing coating, forming a prefabricated coating of a titanium-containing mixture on at least one side of an aluminum foil substrate, and sintering the aluminum foil substrate with the prefabricated coating in an oxygen-isolated atmosphere to obtain the titanium-containing coating consisting of titanium oxide and a carbon material, wherein the titanium-containing mixture comprises a titanium-containing compound and a carbon source, and part of the titanium-containing compound is in a strip shape with the length-diameter ratio not less than 5; and (5) preparing a product.
Examples 1 to 12:
comparative examples 1 to 6:
the electrode foil parameter testing method in the embodiment refers to the electrode foil technical standard (standard number SJ/T11140-:
the static specific volume test method comprises the following steps: referring to the method for measuring the capacitance of the cathode foil in appendix B of the technical standards of the electrode foil, an electrostatic capacitance measuring instrument is used to measure a voltage of less than 0.5Vrms and a frequency of 120Hz + -5 Hz, an ammonium adipate solution (1000 ml of pure water + 150g of ammonium adipate (capacitance grade)) is used as a test solution, and a resistivity (70 ℃ + -2 ℃) is used
pH：(50℃±2℃)
The effective test area of the test sample is 5cm2And the positive and negative test plates are test sample pieces.
The method for testing the electrostatic specific volume and the capacity retention rate after 1h of hydration comprises the following steps: after the specific volume is tested by adopting an electrostatic specific volume test method, a sample wafer is cleaned by pure water, the sample wafer is placed into a pure water tank or a beaker with the temperature of more than or equal to 95 ℃ and is kept for 60+1min, the specific volume is tested by the electrostatic specific volume test method A again, and the retention rate after 1h of hydration is (the specific volume after the hydration test/the specific volume before the test) multiplied by 100 percent.
The method for testing the adhesion of the coating comprises the following steps: adhesion was evaluated by the sticking method (taping).
An adhesive tape (product name Scotch, manufactured by Sumitomo 3M Co., Ltd.) having an adhesive surface with a width of 15mm and a length of 120mm was adhered to the surface of the coating layer of an electrode foil sample with a width of 10mm and a length of 100mm, and then the adhesive tape was peeled off and the adhesion was evaluated by the following equation.
Adhesion (%) } x 100 (the weight of the carbon-containing layer after the drawing (mg) and the weight of the carbon-containing layer before the drawing (mg)).
Coating composition test method:
the content of simple substance carbon (containing shaped carbon, such as carbon nano tube, graphene and the like which are directly added and amorphous pyrolytic carbon) in a quantitative sample is tested by a carbon-sulfur instrument.
An XRD spectrogram is measured by high-precision X-ray diffraction (XRD), and the content proportion of a main phase (titanium oxide) of the coating is quantitatively calculated by peak shape fine modification.
The formation of carbides and oxycarbides in the coating and intermediate layer was evaluated by quantitative analysis of carbides.
The generated gas was collected by dissolving all the electrode foil samples in a 20% NaOH aqueous solution, and the collected gas was quantitatively analyzed by a high sensitivity gas chromatography mass spectrometer (GC-MS) equipped with a flame ionization detector, converted into contents of carbides of aluminum and titanium, and the content of metal ion components in the solution was measured by an inductively coupled plasma spectrometer (ICP). The two data are comprehensively calculated to obtain the total amount of titanium dioxide and carbon-containing compounds (aluminum carbide, titanium carbide, aluminum oxycarbide and titanium oxycarbide) in the electrode foil. The formation of aluminum and the intermediate layer of the coating and the carbon-containing compounds in the coating was evaluated for several days according to the following formula: the content of the carbon-containing compound (containing aluminum carbide, titanium carbide, aluminum oxycarbide, and titanium oxycarbide) was defined as weight (mg)/coating weight (mg) × 100%.
The coating compositions and properties of examples 1-12 and comparative examples 1-6 were measured as follows:
examples 1 to 12:
comparative examples 1 to 6:
from example 1 and comparative example 2 it can be seen that: the coating uses titanium oxide, and compared with the titanium metal (indirectly utilizing a natural oxide film on the surface of the titanium metal), the specific capacity is slightly lower, but higher stability can be obtained (the retention of hydration capacity is only one of the stability characteristics).
As can be seen from example 1 and comparative example 1, the titanium oxide in the coating layer is formed into a network self-woven structure using a long stripe shape with a high aspect ratio (> 5), which can improve the coating layer cohesion, and can achieve both higher coating layer adhesion and effectively improve stability in liquid (such as hydration capacity stability) compared to the particle form.
From example 11 and comparative example 1, it can be seen that the titanium oxide with high aspect ratio is more favorable for forming a network interweaving structure, and even if a small amount of titanium oxide is added, the existence of the weaving network can net the coating particles together, so that the coating cohesion is obviously improved.
As can be seen from example 4 and comparative example 5, when the aspect ratio of the elongated titanium oxide is less than 5, the adhesion and hydration stability of the coating layer are affected, and in combination with comparative example 6, when the aspect ratio of the elongated carbon nanotube is also low, the adhesion of the coating layer is further lowered, accompanied by the weakening of the hydration stability.
From a comparison of example 1 with comparative example 4, example 1 and comparative example 3, it can be seen that: the stability of the titanium oxide can be greatly improved by compounding the titanium oxide with carbon, and the problem that the titanium oxide is singly used in an electrode and has a short plate with poor stability is solved.
From a comparison of examples 1, 2 and 3, it can be seen that the length-diameter ratio of the long titanium oxide has an important influence on the performance, and the improvement of the length-diameter ratio can improve the adhesion and hydration stability of the coating.
Examples 3 and 12 show that the generation of carbon-containing compounds is influenced by the lower heat treatment temperature, and the carbon-containing compounds can be used as a connection reinforcing phase inside the coating and between the coating and the aluminum foil intermediate layer, so that the improvement of the content of the carbon-containing compounds has the improvement effect on the adhesion degree and the hydration stability of the coating.
From examples 4 and 5, it can be seen that the specific capacity can be significantly improved by adding the granular titanium oxide into the strip-shaped titanium oxide, but the adhesion of the coating is lower than that of the pure strip-shaped titanium oxide, and the hydration stability is correspondingly reduced, and from examples 5 and 6, under the condition that the added granular titanium oxide is compounded by large and small particles, the space can be effectively utilized under the condition of the same thickness, higher capacity can be obtained, the weakening degree of the adhesion and the hydration stability of the coating due to the addition of the granular titanium oxide can be reduced, compared with the case that the particle sizes are close, the adhesion of the coating can be improved, and the liquid stability (hydration stability) can be greatly improved.
As can be seen from examples 6 and 7, when the carbon component in the coating layer is in the form of an elongated tube (long strip), carbon nanotubes having a higher aspect ratio are more advantageous for the adhesion of the coating layer and the hydration stability.
It can be seen from examples 8, 9, and 10 that, compared with the uniform and integrated coating, the coating has the grooves for dividing the coating, which can increase the specific volume and is beneficial to enhancing the adhesion of the coating, and this is more significant in the case of thicker coating, when the coating is thicker, the coating at the bottom is difficult to be soaked by the electrolyte to exert the capacity, the grooves provide the channels for soaking the electrolyte, the capacity extraction rate of the bottom in the coating is effectively increased, and the stress release channels of the coating are provided to prevent the thick coating from collapsing integrally.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. The electrode foil is characterized by comprising an aluminum foil substrate and a titanium-containing coating metallurgically bonded on at least one surface of the aluminum foil substrate, wherein the titanium-containing coating is composed of titanium oxide and a carbon material, and at least part of the titanium oxide is strip-shaped oxide with the length-diameter ratio not less than 5; at least one of aluminum carbide or carbon oxide generated in situ is arranged between the aluminum foil substrate and the titanium-containing coating; the titanium-containing coating contains at least one of in-situ generated titanium carbide or titanium oxycarbide; not less than 2 wt% of the titanium oxide is a long oxide having an aspect ratio of not less than 5.
2. The electrode foil of claim 1, wherein the titanium oxide further comprises a particulate oxide having an aspect ratio of less than 3.
3. The electrode foil of claim 2, wherein the particulate oxide has a cumulative 90% particle size (D90) value of 5 to 100 times the cumulative 10% particle size (D10) as determined by laser diffraction scattering particle size distribution.
4. The electrode foil of claim 1, wherein the titanium-containing coating has a fluted texture that integrally segments the titanium-containing coating into discontinuous coatings.
5. The electrode foil of claim 1, wherein the carbon material is in an elongated form having an aspect ratio of not less than 10 at least in part and is distributed in a net-like self-woven structure in the titanium-containing coating layer.
6. The electrode foil as claimed in claim 1, wherein the carbon material is selected from one or more of carbon black, graphite, carbon nanotube, graphene, activated carbon, pyrolytic carbon, carbon fiber, and glassy carbon.
7. An electrolytic capacitor having the electrode foil according to any one of claims 1 to 6 as at least one of a positive electrode and a negative electrode.
8. A method for manufacturing an electrode foil, comprising:
preparing a titanium-containing coating, forming a prefabricated coating of a titanium-containing mixture on at least one side of an aluminum foil substrate, and sintering the aluminum foil substrate with the prefabricated coating in an oxygen-isolated atmosphere to obtain the titanium-containing coating consisting of titanium oxide and a carbon material, wherein the titanium-containing mixture comprises a titanium-containing compound and a carbon source, and at least part of the titanium-containing compound is in a strip shape with the length-diameter ratio not less than 5; not less than 2 wt% of the titanium oxide is a long-strip-shaped oxide having an aspect ratio of not less than 5; and (5) preparing a product.
9. The method of claim 8, wherein the titanium-containing compound is selected from the group consisting of titanium oxides, titanium hydroxides, organic polymers of titanium, titanium halides, and mixtures thereof.
10. The method according to claim 8, wherein the carbon source is at least one of a carbon material, an organic polymer, and a hydrocarbon carbon source.
11. The method according to claim 10, wherein the carbon material is one or more selected from the group consisting of carbon black, graphite, carbon nanotubes, graphene, activated carbon, pyrolytic carbon, carbon fibers and glassy carbon, and the carbon material is in the form of a strip having an aspect ratio of at least 10.
12. The production method according to claim 8, wherein the titanium oxide further comprises a particulate oxide having an aspect ratio of less than 3.
13. The production method according to claim 12, wherein the particulate oxide has a cumulative 90% particle diameter (D90) value 5 to 100 times the cumulative 10% particle diameter (D10) as measured by laser diffraction scattering particle size distribution measurement.
14. The method of claim 8, wherein the oxygen-excluded atmosphere in the step of forming the titanium-containing coating layer is a reducing atmosphere.
15. The method of claim 8, wherein the step of forming the titanium-containing coating layer comprises at least one of heating sintering, laser sintering, spark sintering, electromagnetic induction sintering, spark plasma sintering, high pressure sintering, and pulsed light sintering.
16. The method of claim 15, wherein the step of forming the titanium-containing coating layer comprises sintering with heat at a temperature of 300 to 640 ℃.
17. The manufacturing method according to claim 8, wherein the step of manufacturing the titanium-containing coating layer comprises a step of subjecting the titanium-containing mixture and a solvent to a high-energy activation step in a container, wherein the high-energy activation step is at least one of high-pressure fluid jet milling, hammer milling, rod milling, ball milling, sand milling and high-speed shearing, and the obtained slurry is used for forming the coating layer on the surface of the aluminum foil base body by means of coating, spraying, printing or hot pressing.
18. The method of manufacturing according to claim 8, wherein the step of forming the titanium-containing coating layer includes a step of forming a groove pattern for dividing the titanium-containing coating layer into discontinuous coating layers as a whole.
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