ELECTRODE MATERIAL, SOLID ELECTROLYTIC CAPACITOR, CATHODE SHEET FOR USE IN A SOLID ELECTROLYTIC CAPA

专利摘要:
electrode material, solid electrolytic capacitors, and non-aqueous electrolytic double layer electrical capacitors, cathode sheet, current collector, positive, negative electrodes, and for a non-aqueous electrolytic double layer electrical capacitor, and non-aqueous electrolytic secondary battery is Described is a negative electrode sheet for a solid electrolytic capacitor that increases capacitance, reduces esr and current leakage, increases heat resistance and reduces manufacturing costs, and improves power density, achieves fast charge/discharge, and increases Lifetime characteristics of energy storage elements such as rechargeable batteries, electric double layer capacitors and hybrid capacitors. a negative electrode sheet or a current collector are used which: are obtained by forming a metal layer, a mixed layer obtained by mixing a material constituting the metal layer with carbon and a carbon layer substantially comprising , carbon in a sheet of metal; and are configured in such a way to change as the components of the blended layer change from a component containing only the material substantially constituting the metal layer to a component containing substantially only carbon, and the layer of metal to the carbon layer.
公开号:BR112013021247B1
申请号:R112013021247-0
申请日:2012-02-20
公开日:2021-06-22
发明作者:Mitsuo Yoshimura；Koji Yoshioka
申请人:Japan Capacitor Industrial Co., Ltd；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[01] The present invention concerns a solid electrolytic capacitor with a solid electrolyte layer (typically, an electrically conductive polymer layer) formed inside it and an electrode sheet usable in a type of capacitor like this. The present invention further relates to a current collector, an electrode and an electrical energy storage element, such as a secondary battery, an electrical double layer capacitor or a hybrid capacitor, which uses the electrode. FUNDAMENTALS OF THE INVENTION (Fundamentals of the Invention in relation to the Solid Electrolytic Capacitor)
[02] In recent years, operating frequencies of electronic devices have become increasingly higher. Along with this trend, an electrolytic capacitor as an electronic component also needs to be provided as a product with excellent impedance properties in a higher operating frequency range than before. In order to address the need, several solid electrolytic capacitors that use, like a solid electrolyte, an electrically conductive polymer with a high electrical conductivity, have been developed. This type of solid electrolytic capacitor is excellent particularly in high frequency properties, in addition to service life and temperature properties, and thus widely used in electrical circuits for personal computers, and still other applications.
[03] In a simpler example, a coiled-type solid electrolytic capacitor can be produced by a process comprising a step (i) of: subjecting a surface of an anode aluminum sheet to a chemical conversion treatment to form a oxide film; laminating the resulting aluminum anode sheet to an aluminum cathode sheet using a separator sheet; connect a lead element to each of the two sheets; and winding the laminate to prepare a capacitor element, and a step (ii) of: placing the prepared capacitor element in an aluminum casing; immersing the capacitor element in a solution of the electrically conducting polymer to cause thermal polymerization of an electrically conducting polymer under heat to form a layer of solid electrically conducting polymer between the two sheets. When the anode aluminum sheet is used as an anode, and the cathode aluminum sheet and the electrically connected polymer layer electrically conductive on the cathode aluminum sheet are used as a cathode, the anode and cathode are connected through the electrically insulating oxide film, so that charge and discharge between the anode and the cathode can be achieved.
[04] In the exposed solid electrolytic capacitor, the aluminum foil cathode is not subjected to a chemical conversion treatment, so that no artificially formed oxide film exists on it. However, actually, an oxide film is also formed on the aluminum cathode sheet, due to natural oxidation during production or use. In this case, the solid electrolytic capacitor is generally formed in a layered structure comprising (i) the aluminum anode sheet, (ii) the oxide film on the anode aluminum sheet, (iii) the conductive layer electrical, (iv) the natural oxide film on the aluminum cathode sheet, and (v) the aluminum cathode sheet. This is equivalent to a state where two capacitors are connected in series to each other, which causes a problem where a capacitance of the solid electrolytic capacitor as a whole is reduced.
[05] In order to deal with this problem, research has been conducted to prevent a capacitance component from being generated in a cathode, thus allowing an increase in the capacitance of a capacitor. In this regard, some cathode sheets obtained from conventional surveys and a problem involved with conventional cathode sheets will be described below.
[06] Patent Documents 1 and 2 disclose a cathode sheet obtained by forming a chemical conversion coating film on a surface of an aluminum cathode sheet and by further forming a metal nitride such as TiN, or a metal carbide, such as TiC, in the coating film by chemical conversion by vapor deposition. However, a metal such as Ti, and a nitride or carbide thereof, have insufficient thermal oxidation resistance. Thus, in the cathode sheet, there is a problem in which an oxide film will grow through a heat treatment included in a capacitor production process, resulting in the generation of a capacitance component and an increase in ESR (Equivalent Series Resistance) .
[07] Patent Document 3 discloses a cathode sheet obtained by forming a carbon film on a metal surface with a valve function. However, when a carbon film is directly formed into a metal sheet, such as aluminum foil, there is a problem where an ESR increases due to poor adhesion between the metal sheet and the carbon film.
[08] Patent Document 4 discloses a cathode sheet obtained by forming a carbon-containing layer on a surface of an aluminum sheet, in which an interposed layer consisting of fibrous or filamentary aluminum carbide (Al4C3, aluminum sheet aluminum carbide) is formed between the surface of the aluminum sheet and the carbon-containing layer to provide better adhesion between them. However, in this cathode sheet, the carbon-containing layer is a layer consisting of carbon in particulate form, so that the surface of the aluminum sheet and the carbon-containing layer come into point contact with each other. Thus, there is a problem where an interfacial resistance increases due to the small contact area. Additionally, the carbon-containing layer is formed by a process of applying a carbon-containing substance to the surface of the aluminum sheet and attaching carbon particles onto it through a thermal drying treatment, which causes difficulty in the formation of the layer. which contains carbon to have a sufficiently small thickness and also gives rise to a problem where an electron transfer distance between the Al layer and a solid electrolyte layer becomes larger, thereby causing an increase in ESR. Furthermore, this cathode sheet is insufficient in the property of resisting water (water resistance) and particularly in high temperature environments, a problem occurs where the aluminum carbide foil as an electron transfer path is cut, causing deterioration in electrical conductivity.
[09] Patent Document 5 discloses a cathode sheet obtained by forming, by a vacuum vapor deposition method, a layer of Ni on a wrinkled surface of an aluminum sheet. The description in Patent Document 5 says that a Ni oxide film formed on a surface of the Ni layer is a semiconductor, that is, it has electrical conductivity, which makes it possible to carry out a lower ESR in a capacitor. However, the deterioration in electrical conductivity due to the formation of the oxide film cannot be negligible, and a semiconductor is unsuitable as a component substance in the film. It is desirable that at least one top layer of the film be formed using an electrically conductive substance excellent in the property of resisting oxidation (oxidation resistance).
[010] As another type of cathode sheet for use in an electrolytic capacitor configured to operate using an electrolytic drive solution rather than a solid electrolyte, Patent Document 6 discloses a cathode sheet obtained by vapor deposition of a metal, such as Ti, on a wrinkled surface of an aluminum sheet to form a metal film thereon, and further application of a binder with fine carbon particles dispersed over it, wherein the applied binder is subjected to a heat treatment. to fix the fine carbon particles in the metal film. However, in the cathode sheet described in Patent Document 6, a surface of the Ti film is oxidized by the electrolytic drive solution so that a high resistance is generated at an interface between a layer composed of the Ti film and a layer that consists of carbon, causing an increase in the ESR of a capacitor (it is mentioned that, in order to suppress an influence of Ti oxidation, the cathode sheet described in Patent Document 6 is preferably subjected to a wrinkling treatment of the surface, such as engraving). Furthermore, assuming it is used as a solid electrolytic capacitor, an oxide film will grow through a heat treatment included in a capacitor production process, causing an increase in ESR. Additionally, when the Ti film is associated with carbon by a binder or the like, a large interfacial resistance is also generated in an associated part, causing an increase in the ESR of a capacitor.
[011] In general, it is described that, in a solid electrolytic capacitor, when a surface of a cathode sheet is appropriately corrugated, an area of contact with a solid electrolyte becomes larger and, thus, the ESR is reduced. However, the effect is small. Furthermore, when a surface of an aluminum substrate is wrinkled, for example, by an etching treatment, a space occurs between the aluminum substrate and a film formed within the pores resulting from the surface wrinkling, so that the surface is unstable due to a reaction that takes place in space by a chemical agent and water used in a capacitor production process, and an interface between the aluminum substrate and the film is more likely to be oxidized by oxygen diffusion from this mode, causing problems such as an increase in interfacial resistance and acceleration in the degradation of a capacitor. Additionally, there is another problem where the surface roughening treatment leads to an increase in capacitor production cost.
[012] As stated, in conventional cathode sheet where a metal film is formed on an aluminum sheet, there is a problem where a surface of the film is oxidized, so that when an oxidation reaction progresses due to the change temporal or the like, a cathode has a capacitance. Additionally, in conventional cathode sheet where a carbon layer is formed on an aluminum sheet directly or through a metal film or the like, if adhesion between the layers is insufficient, a surface of the aluminum sheet or a surface of the metal layers in contact with carbon are oxidized, so that a cathode has a capacitance. Therefore, a capacitance of a solid electrolytic capacitor is reduced as a whole in the way previously mentioned. Furthermore, each of the exposed conventional cathode sheets has problems such as an increase in ESR and an increase in costs. (Fundamentals of the Invention in relation to the Secondary Battery, the Double Electric Layer Capacitor, the Hybrid Capacitor, etc.)
[013] In recent years, in view of the multifunctionalization of mobile electronic devices, improved fuel economy of automobiles and transport and construction vehicles, diffusion of distributed renewable energy, upgrade and expansion of backup power supply in case of disaster / emergency , etc., demand for an electrical energy storage element to be mounted therein has increased over the years. In the electric energy storage element which includes a double electric layer capacitor, a hybrid capacitor and a secondary battery, there is a need to further improve a property of power density (W/kg, W/L) and service life.
[014] In view of performance, such as resistance and electrical conductivity of treatment / processing, productivity, production costs, etc., a current collector composed of a metal sheet is used in an electrode that constitutes the storage element of electricity in many cases. The electrode is constructed by forming, in a current collector, an electrode layer comprising an active substance, an electrically conductive auxiliary and a binder. When adhesion, electrical conductivity and/or chemical stability between the current collector and the electrode layer are insufficient, a satisfactory power density cannot be obtained due to an increase in contact resistance, thereby causing difficulty in rapid charging / discharge. Additionally, for example, together with a charge-discharge cycle of the electrical energy storage element, it is likely that an interface between the current collector and the electrode layer will be transformed over time due to a chemical change such as oxidation. , or it is likely that the electrode layer will be peeled off of the current collector, thereby causing an increase in internal resistance and a reduction in service life.
[015] In this regard, for example, Patent Document 7 describes a battery obtained by forming a layer of carbon film between a current collector and a layer of the active substance.
[016] However, when the carbon film layer is directly formed on the metal sheet, adhesion, electrical conductivity, and chemical stability between the metal sheet and the carbon film layer are insufficient, so that a contact resistance between the current collector and the electrode layer increases gradually, which leads to problems such as a reduction in power density and an increase in internal resistance, thereby causing difficulty in rapid charge/discharge. Furthermore, according to the inventors' research, there are Patent Documents 8 through 11 as related documents of the prior art. However, movie settings disclosed in them have the same problems. LIST OF PREVIOUS TECHNOLOGY DOCUMENTS
[017] PATENT DOCUMENTS Patent Document 1: JP 2007-036282 A Patent Document 2: JP 2007-019542 A Patent Document 3: JP 2006-190878 A Patent Document 4: JP 2006-100478 A Patent Document 5 : JP 2009-049376 A Patent Document 6: JP 2007-095865 A Patent Document 7: JP 11-250900 A Patent Document 8: JP 2011-142100 A Patent Document 9: JP 2010-218971 A Patent Document 10 : JP 2009-283275 A Patent Document 11: JP 2008-270092 A SUMMARY OF THE INVENTION TECHNICAL PROBLEM
[018] The present invention was made to solve the conventional technical problems exposed. Specifically, in a cathode sheet for a solid electrolytic capacitor, which is obtained by forming a film on an aluminum sheet, it is an objective of the present invention to prevent the generation of a capacitance in a cathode by increasing the oxidation resistance of each layer constituting the film and the adhesion between the respective layers. In this type of cathode sheet, it is another objective of the present invention to prevent the generation of a large interfacial resistance due to a rapid change in film composition, thereby allowing a reduction in the ESR and LC (Leakage Current) of a capacitor.
[019] Additionally, in order to solve the problems of conventional techniques disclosed in Patent Documents 7 through 11 to minimize an increase in internal resistance over a long period of time and maintain a high power density, thereby allowing fast charging / discharge and realizing an electrical energy storage element with excellent service life property, it is yet another objective of the present invention to improve adhesion and electrical conductivity between a current collector and an electrode layer, and to suppress the transformation of a interface between the current collector and the electrode layer due to a chemical change. SOLVING THE TECHNICAL PROBLEM
[020] In order to solve the above problems, the present invention provides an electrode material that is characterized in that it is constructed by forming, on an electrode substrate, a first electrically conductive layer, a mixed layer that contains carbon and a substance that makes up the first electrically conductive layer in a mixed state, and a second electrically conductive layer consisting substantially of carbon, wherein the blended layer is configured to have a composition that changes from a state that substantially contains just the substance that makes up the first electrically conductive layer to a state that contains substantially only carbon, in a direction from the first electrically conductive layer to the second electrically conductive layer.
[021] In the electrode material provided by the present invention, the mixed layer containing respective components of the first and second electrically conductive layers in a mixed state is formed between the two electrically conductive layers, so that it is possible to improve the adhesion between the substance that makes up the first electrically conductive layer and carbon. This feature solves the conventional technical problem that, due to insufficient adhesion between carbon and the substance that makes up the first electrically conductive layer, the substance that makes up the first electrically conductive layer is oxidized, thereby causing the material to electrode has a capacitance, and additionally causing an increase in ESR. Furthermore, the second electrically conductive layer consists substantially of carbon so that it has excellent oxidation resistance. Additionally, in a boundary region with the first electrically conductive layer, the blended layer contains substantially only the substance that makes up the first electrically conductive layer, whereas, in a boundary region with the second electrically conductive layer, the blended layer contains, substantially, just carbon. This avoids the problem that an electrode material composition changes rapidly in the boundary region, thereby causing the generation of a large interfacial resistance.
[022] In the foregoing description, the term "containing substantially only the substance that makes up the first electrically conductive layer" does not necessarily mean that absolutely no component other than the substance that makes up the first electrically conductive layer is contained. For example, depending on: limitations in production techniques regarding the control of the purity of each component in each layer and the mixture of impurities; and a capacitance level as a permissible error of the electrode material in each product, an actual composition in the boundary region between the mixed layer and each of the electrically conductive layers can change variably. The same applies to the terms "consisting substantially of carbon" and "containing substantially only carbon".
[023] Additionally, in the foregoing description, the term "the mixed layer is configured to have a composition that changes from a state that contains substantially only the substance that makes up the first electrically conductive layer to a state that contains substantially only carbon, in a direction from the first electrically conductive layer to the second electrically conductive layer" does not necessarily mean that a rate of carbon content in the mixed layer increases monotonically in the direction from the first electrically conductive layer to the second electrically conductive layer. For example, depending on a variation in each component concentration brought about by limitations in production techniques, an actual composition at each position in the blended layer may change variously. However, it is preferable that the blended layer be formed to allow the rate of carbon content to continuously increase towards the first electrically conductive layer to the second electrically conductive layer.
[024] The first electrically conductive layer can contain at least one element selected from the group consisting of Ta, Ti, Cr, Al, Nb, V, W, Hf, Cu, metal nitrides and metal carbides. A substance usable in the first electrically conductive layer constituting the electrode material of the present invention is not limited to exposed substances. However, in the case where an aluminum substrate is used as the electrode substrate, in view of energy efficiency and adhesion with the aluminum substrate, it is preferable to use the exposed substances and particularly to use a metal such as Ti and Al (provided adhesion with the substrate or electrical conductivity in the first electrically conductive layer is not impaired, a plurality of elements, such as an alloy, may be contained). It is understood that a usable material as the electrode substrate is not limited to aluminum but can be any suitable material such as Ta, Ti or Nb, such as a metal with a valve function; or an aluminum alloy prepared by adding any such materials to aluminum.
[025] In the electrode material of the present invention, it is not an essential requirement to wrinkle a surface of the electrode substrate. As described in the following Examples based on performance test data, even if an electrode substrate is not subject to surface wrinkling during the preparation of the electrode material of the present invention, a solid electrolytic capacitor using the electrode substrate has excellent capacitance, ESR and current leakage properties compared to before. In particular, the following examples show that the electrode substrate of the present invention prepared without subjecting an electrode substrate to surface wrinkling has excellent heat-resistance property (heat resistance) compared to an electrode material with an electrode substrate. electrode with wrinkled surface.
[026] The present invention also provides a solid electrolytic capacitor comprising an anode sheet, a cathode sheet, a separator provided between the anode and cathode sheets, and a solid electrolyte layer formed between the anode and cathode sheets. cathode. Solid electrolytic capacitor is characterized in that the aforementioned electrode material is used as the cathode sheet.
[027] The electrode material of the present invention is particularly suitable for use as a cathode sheet in a solid coiled type or stacked type electrolytic capacitor. In contrast, it is usable on a number of capacitors, including an electrolytic capacitor configured to operate using an electrolytic solution, a double-layer electrical capacitor, a lithium ion capacitor, a lithium ion battery, a solar battery, and others.
[028] Specifically, the electrode material of the present invention can be modified by additionally forming a layer consisting of activated carbon in the second electrically conductive layer consisting substantially of carbon. The resulting electrode material can be used as a positive or negative electrode for an electric double layer capacitor (the electrode material modified with this configuration can be used as a positive electrode for a lithium ion capacitor without any change). Additionally, the electrode material of the present invention can be modified by further forming a layer consisting of an active substance containing Li in the second electrically conductive layer. The resulting electrode material can be used as a positive electrode for a lithium ion battery.
[029] That is, the electrode material of the present invention can be used as an electrode as it is or can be used as an anode or cathode (positive or negative electrode) of any storage device in an additionally modified state, if necessary , such as in a state where an additional layer is formed as set out.
[030] The solid electrolyte layer can contain at least one element selected from the group consisting of manganese dioxide (MnO2), tetracyanoquinodimethane (TCNQ), polyethylenedioxythiophene (PEDOT), polyaniline (PANI) and polypyrrole. However, any suitable electrolyte other than these can also be used. As an example, the formation of a solid electrolyte layer consisting of PEDOT can be accomplished by heating a capacitor element while immersing it in a mixed solution of 3,4-ethylenedioxythiophene, p-toluenesulfonic acid and iron(II) salt ), to thermally polymerize an electrolyte.
[031] As a typical embodiment of the electrode material, the present invention provides a cathode sheet for use in a solid electrolytic capacitor with a capacitor element comprising an anode sheet, a cathode sheet, a separator provided between the sheets of anode and cathode, and a solid electrically conductive polymer layer formed between the anode and cathode sheets. The cathode sheet is characterized in that it comprises: an aluminum sheet with an unwrinkled surface; a metal layer formed on the aluminum sheet and consisting substantially of Ti or Al; a blended layer formed on the metal layer and containing carbon and Ti or Al in a blended state; and a carbon layer formed in the blended layer and consisting substantially of carbon, wherein the blended layer is configured to have a composition that changes from a state containing substantially only Ti or Al to a state containing substantially , just carbon, in one direction from the metal layer to the carbon layer.
[032] This cathode sheet corresponds to a typical embodiment of the present invention that will be described in the following examples based on performance test data. However, it is apparent that a modality for solving the aforementioned conventional technical problems is not limited to this one.
[033] For example, as is evident from the following performance tests, even when an aluminum substrate in the cathode sheet of the present invention has a ridged surface, a solid electrolytic capacitor using it has excellent properties compared to before, in terms of capacitance, etc., and a usable material as the electrode substrate is not limited to aluminium, as previously mentioned. With respect to a material for use in the metal layer, it is also preferable to use Ti or Al, in view of adhesion with aluminium. However, any other material with excellent adhesion to aluminum, such as Ta or Cr, can also be used. Additionally, when an electrode substrate made of a different material is used, the metal layer can be formed using a material suitable for the substrate. For example, when a copper sheet is used as the electrode material, a metal layer consisting of Cr with excellent adhesion with the copper sheet can be formed, for example, by ionic metallization. In this case, it is considered that Cr penetrates through a natural oxide film on a surface of the copper sheet and binds directly to the sheet cover, and that this provides high electrical conductivity, while suppressing the generation of a capacitance component, of accordingly, it becomes possible to obtain the same properties as in the case where the metal layer consisting of Ti or Al is formed in an aluminum foil.
[034] In the cathode sheet of the present invention, the blended layer containing respective components of the metal layer and the carbon layer in a blended state is formed between the two layers. It is apparent that the improvement in metal-carbon adhesion based on the introduction of the exposed mixed layer can be obtained in the same way as in the case where the metal layer is formed using a material other than Ti or Al, and it is considered that the better adhesion makes it possible to prevent the formation of an oxide film on the metal and suppress the generation of a capacitance in the cathode sheet. Additionally, in a boundary region with the metal layer, the blended layer contains substantially only Ti or Al, whereas, in a boundary region with the carbon layer, the blended layer contains substantially only carbon. Thus, it is apparent that the effect of preventing rapid compositional changes in the boundary regions to suppress an interfacial resistance at a low level can be obtained in the same way as in the case where the metal layer is formed using a material other than Ti or Al .
[035] Additionally, in order to solve the problems of conventional techniques disclosed in Patent Documents 7 to 11, the present invention provides a current collector for an electrode, which is characterized in that it is constructed by forming, on a substrate that contains a metal, a first electrically conductive layer that contains a metal, a mixed layer that contains carbon and a substance that makes up the first electrically conductive layer that contains a metal in a mixed state, and a second electrically conductive layer consisting of, substantially of carbon, wherein the blended layer is configured to have a composition that changes from a state that contains substantially only the substance that makes up the first electrically conductive layer that contains a metal to a state that contains substantially only carbon , in a direction from the first electrically conductive layer containing a metal to the second electrically conductive layer.
[036] In the current collector provided by the present invention, the first electrically conductive layer containing a metal and the mixed layer containing respective components of the first electrically conductive layer containing a metal and the second electrically conductive layer consisting substantially of carbon, in a mixed state, are formed between the surface of the substrate containing a metal and the second electrically conductive layer, so that it is possible to improve the adhesion between the substrate and the first electrically conductive layer, and the adhesion between the first layer electrically conductive and the electrically conductive second layer, thereby improving electrical conductivity and chemical stability at each interface. This feature solves the conventional technical problem that, due to insufficient adhesion between the substrate and carbon and insufficient electrical conductivity at an interface and chemical stability at an interface, a contact resistance between the current collector and the layer of electrode increases and, together with repeated use, an internal resistance of the current collector increases, causing a reduction in the electrode power density. Furthermore, the second electrically conductive layer consists substantially of carbon so that it has excellent electrical conductivity and resistance to chemical change such as oxidation. Additionally, in a boundary region with each of the first and second electrically conductive layers, a region of the layer mixed on the side of the first electrically conductive layer contains only the substance that makes up the first electrically conductive layer, while a region of the layer blended in the The side of the second electrically conductive layer contains substantially only carbon. This avoids the problem that a rapid change in composition occurs in the boundary region, thus causing the generation of a great interfacial resistance.
[037] In the foregoing description, the term "containing substantially only the substance that makes up the first electrically conductive layer that contains a metal" does not necessarily mean that absolutely no component other than the substance that makes up the first electrically conductive layer that contains a metal is contained. For example, depending on: limitations in production techniques regarding the control of the purity of each component in each layer and the mixture of impurities; and a level of adhesion or contact resistance as a permissible error of the current collector in each product, an actual composition in the boundary region between the mixed layer and each of the electrically conductive layers may change variably. The same applies to the terms "consisting substantially of carbon" and "containing substantially only carbon".
[038] Additionally, in the foregoing description, the term "the mixed layer is configured to have a composition that changes from a state that contains substantially only the substance that makes up the first electrically conductive layer that contains a metal to a state that contains , substantially, only carbon, in a direction from the first electrically conductive layer containing a metal to the second electrically conductive layer" does not necessarily mean that a rate of carbon content in the mixed layer increases monotonically in the direction of the first electrically conductive layer to the second electrically conductive layer. For example, depending on a variation in each component concentration brought about by limitations in production techniques, an actual composition at each position in the blended layer may change variously. However, it is preferable that the blended layer be formed to allow the rate of carbon content to continuously increase towards the first electrically conductive layer to the second electrically conductive layer.
[039] The first electrically conductive layer can contain at least one element selected from the group consisting of Ta, Ti, Cr, Al, Nb, V, W, Hf, Cu, metal nitrides and metal carbides. A substance usable in the first electrically conductive layer constituting the current collector of the present invention is not limited to exposed substances. However, in the case where an aluminum foil is used as the substrate that contains a metal, in view of energy efficiency and adhesion with the aluminum foil, it is preferable to use the exposed substances and particularly to use a metal such as Ti and Al (provided adhesion with the substrate or electrical conductivity in the first electrically conductive layer is not impaired, a plurality of elements, such as an alloy, may be contained).
[040] Carbon for use in the electrically conductive second layer is not particularly limited. However, in view of increasing a power density of an electrical energy storage element, it is preferable to use graphite-like carbon, which has particularly excellent electrical conductivity, among carbon materials. It is also preferable to use it in view of production costs. As used herein, the term "graphite-like carbon" means carbon with an amorphous structure in which two types of bonds: diamond bond (carbon-carbon bond based on sp3 hybrid orbital); and graphite bonding (carbon-carbon bonding based on sp2 hybrid orbital); they exist in a mixed state, in which a graphite bond rate is above one-half. However, in addition to the amorphous structure, a phase with a crystal structure partially composed of a graphite structure (ie, hexagonal crystal structure composed of bonds based on sp2 hybrid orbital).
[041] A usable material as the substrate that contains a metal is not limited to aluminum but can be a sheet metal made of any suitable material such as Ti, Cu, Ni, Hf, stainless steel or an aluminum alloy prepared by adding any such materials to aluminum. A sheet metal as a current collector for use in a positive electrode and a negative electrode of each electrical energy storage element is selected in view of electrochemical stability, electrical conductivity, weight, processability, production costs and others, still considering an electrolyte and an operational potential of an active substance. When the electrical energy storage element is an electrical double layer capacitor, it is preferable to use aluminum foil for both positive and negative electrodes. When it is a hybrid capacitor or secondary battery, it is preferable to use aluminum foil for a positive electrode and to use aluminum or copper foil for a negative electrode.
[042] In the current collector of the present invention, it is not an essential requirement to crimp a substrate surface that contains a metal. However, as described in the following examples based on performance test data, when the substrate is subjected to surface wrinkling during the preparation of the current collector of the present invention, the adhesion between the current collector and the electrode layer and collection capabilities are improved, which is more beneficial for improving power density and lifetime properties. This largely stems from the improvement in adhesion strength based on a physical anchor effect between the current collector and the electrode layer, and a contact resistance reduction effect based on an increase in the contact area between them, in addition to of the aforementioned effects of the first electrically conductive layer containing a metal, the blended layer, and the second electrically conductive layer. Particularly, in a hybrid capacitor and a secondary battery where an active substance repeats the volume expansion and contraction brought about by occlusion (intercalation) and release (deintercalation) of ions, wrinkling of the substrate surface is more effective. The means for surface wrinkling is not limited. However, when an aluminum or copper foil is used as a material for the substrate, as mentioned above, it is preferable to perform surface roughening, for example, by chemical or electrochemical etching using an acidic or alkaline solution, which is a method able to facilitate the achievement of an effective porous structure to improve adhesion based on an anchor effect with the electrode layer and with excellent productivity. On a hybrid capacitor, such as a lithium ion capacitor, and a secondary battery, such as a lithium ion secondary battery, when it is necessary to perform a pre-doping operation to allow alkali metal ions or metal ions alkaline earth are uniformly clogged in an active substance from a positive electrode and/or a negative electrode in the electrical energy storage element, a through hole may be provided in the metal sheet, depending on a type of production technique and the convenience of production.
[043] A total thickness of the layers including the mixed layer from the first electrically conductive layer to the second electrically conductive layer is not particularly limited. For example, this thickness can be set to 45 nm or less. In this case, it becomes possible to prevent an electron transfer distance between the current collector and the electrode layer from getting larger, thereby further improving the effect of reducing the internal resistance. Particularly, when the sheet metal is subjected to surface wrinkling, the current collector can be prepared to allow the overall thickness to be thinned out. This makes it possible to prevent a film formed in the current collector from filling a fine and delicate porous structure formed in the sheet metal by engraving or the like, and weaken the anchor effect and the effect of increasing the contact area, and uniformly form the first and the second electrically conductive layers in an inner wall with the porous structure. In the case where the current collector is used in a negative electrode of a hybrid capacitor or a secondary battery, the carbon itself that makes up the second electrically conductive layer can serve as an active substance capable of blocking and releasing alkali metal ions or ions of alkaline earth metal. In this case, in order to obtain sufficient power density (Wh/kg, Wh/L) as an electrical energy storage element, an electrode layer containing active substance is required to have a layer thickness of at least 1 µm or more. However, in view of productivity, production costs, etc., it is undesirable to form the second electrically conductive layer to have a thickness of about 1 µm for the purpose of using it as an active substance. Preferably, an electrode layer containing active substance is formed as a separate layer from the second electrically conductive layer constituting the current collector of the present invention.
[044] The present invention provides a secondary battery, such as a lithium ion secondary battery, a sodium ion secondary battery, a magnesium ion secondary battery or a calcium ion secondary battery, comprising: an electrode positive formed with an electrode layer comprising an active substance that includes a transition metal oxide or transition metal phosphate compound that contains an alkali metal or an alkaline earth metal, an electrically conductive auxiliary, and a binder; and a negative electrode formed with an electrode layer comprising an active substance that includes at least one element selected from the group consisting of a carbon material capable of occluding and releasing an alkali metal ion or earth alkali metal ion, Sn, Si or silicon oxide, S or sulfide, and titanium oxide, an electrically conductive auxiliary and a binder. The secondary battery is characterized in that it comprises an electrode that uses the exposed current collector, where the electrode is used as the positive electrode and the negative electrode. In this case, for example, the transition metal oxide or transition metal phosphate compound that contains an alkali metal or an alkaline earth metal, which is included in the active substance of the positive electrode used in the exposed secondary battery, includes LiCoO2. LiMn2O4, LiNiO2, Li(Ni-Mn-Co)O2, Li(Ni-Co-Al)O2, LiFePO4, NaCrO2, NaFeO2, MgHf(MoO4)3, Ca3Co2O6 and Ca3CoMnO6.
[045] The present invention provides an electrical double layer capacitor that uses: a positive electrode formed with an electrode layer comprising an active substance that includes activated carbon or carbon nanotube, an auxiliary electrical conductor and a binder; and a negative electrode formed with the same layered structure. The electric double layer capacitor is characterized in that it comprises an electrode that uses the exposed current collector, where the electrode is used as the positive electrode and the negative electrode.
[046] Additionally, the present invention provides a hybrid capacitor, such as a lithium ion capacitor, which comprises a positive electrode formed with an electrode layer comprising an active substance that includes activated carbon or carbon nanotube, a conductive auxiliary electric and a binder; and a negative electrode formed with an electrode layer comprising an active substance that includes at least one element selected from the group consisting of a carbon material capable of occluding and releasing an alkali metal ion or earth alkali metal ion, Sn, Si or silicon oxide, S or sulfide, and titanium oxide, an electrically conductive auxiliary and a binder. The hybrid capacitor is characterized in that it comprises an electrode that uses the exposed current collector, where the electrode is used as the positive electrode and the negative electrode. EFFECT OF THE INVENTION
[047] In the electrode material of the present invention, interlayer adhesion is improved by the formation of the mixed layer between the first and second electrically conductive layers formed on the electrode substrate, so that it is possible to prevent the oxidation of the substance that makes up the first electrically conductive layer. Furthermore, in a boundary region between the blended layer and each of the first and second electrically conductive layers, the blended layer substantially consists of only one component of a respective layer of the first and second electrically conductive layers, which prevents a increase in interfacial resistance due to a rapid change in the composition of the electrode material in the boundary region. The use of this electrode material as a cathode sheet allows a solid electrolytic capacitor to achieve an increase in capacitance and a reduction in ESR and current leakage.
[048] Furthermore, as shown by the following performance test data, the electrode material of the present invention has extremely excellent heat resistance, so that it is almost without deterioration in quality even after being used under high temperature by a long period of time. Additionally, even when a thickness of a film composed of the first electrically conductive layer, the mixed layer and the second electrically conductive layer and formed on an aluminum substrate is reduced to about 0.02 µm, there is almost no deterioration in the properties of a sheet. of cathode in the electrode material of the present invention is observed and, during the preparation of the cathode sheet, there is no need to wrinkle a surface of the electrode substrate, so that it is possible to reduce a material to be used, and to simplify a process thereby significantly reducing production costs. When the film is formed to have such a reduced thickness, this reduces a risk that breakage will occur during the winding of the cathode sheet. Furthermore, when the film is formed to have such a reduced thickness, an electron transfer distance between the electrode substrate and the solid electrolyte is reduced, so that it is possible to further reduce the ESR.
[049] In the current collector of the present invention, the interlayer adhesion and electrical conductivity, and chemical stability, are improved by the formation of the mixed layer between the first and second electrically conductive layers formed on the electrode substrate, so that it is It is possible to prevent transformation due to a chemical change, such as oxidation, in each of the substrate surface and the substance that makes up the first electrically conductive layer. Furthermore, in a boundary region between the blended layer and each of the first and second electrically conductive layers, the blended layer substantially consists of only one component of a respective layer of the first and second electrically conductive layers, which prevents a increase in interfacial resistance due to a rapid change in the composition of the electrode material in the boundary region. A positive or negative electrode obtained by forming, on the exposed current collector, an electrode layer comprising an active substance, an auxiliary electrical conductor and a binder has excellent electrical conductivity, ability to collect the electrode layer in the current collector, and chemical stability, and is able to maintain high adhesion between the current collector and the electrode layer for a long period of time. In an electrical energy storage element, such as a secondary battery, a double-layer electrical capacitor, or a hybrid capacitor, which uses the exposed electrodes, it becomes possible to improve a power density while minimizing a voltage drop during charging. / discharge and suppressing an element temperature rise during charge / discharge with a large current. Thus, rapid loading/unloading can be carried out continuously over a long period of time to achieve a significant extension of the useful life of the load-unload cycle. BRIEF DESCRIPTION OF THE DRAWINGS
[050] FIG. 1 is a sectional view illustrating a layered structure of a cathode sheet in accordance with an embodiment of the present invention.
[051] FIG. 2 is an exploded diagram illustrating a structure of a coiled-type solid electrolytic capacitor in accordance with an embodiment of the present invention.
[052] FIG. 3 is a graph for comparing measured capacitances in respective samples of a solid electrolytic capacitor using a sheet cathode according to an embodiment of the present invention and a solid electrolytic capacitor using a conventional cathode sheet.
[053] FIG. 4 is a graph for comparing ESRs measured in respective samples of a solid electrolytic capacitor using a sheet cathode according to an embodiment of the present invention and a solid electrolytic capacitor using a conventional cathode sheet.
[054] FIG. 5 is a graph for comparing current leaks measured in respective samples of a solid electrolytic capacitor using a sheet cathode according to an embodiment of the present invention and a solid electrolytic capacitor using a conventional cathode sheet.
[055] FIG. 6 is a graph for comparing rates of change of capacitances before and after testing measured by subjecting, to a heat resistance test, respective samples of a solid electrolytic capacitor using a cathode sheet in accordance with an embodiment of the present invention and a solid electrolytic capacitor that uses a conventional cathode sheet.
[056] FIG. 7 is a graph for comparing rates of change of ESRs before and after testing measured by subjecting, to a heat resistance test, respective samples of a solid electrolytic capacitor using a cathode sheet in accordance with an embodiment of the present invention and a solid electrolytic capacitor that uses a conventional cathode sheet.
[057] FIG. 8 is a sectional view illustrating a layered structure of a current collector in accordance with an embodiment of the present invention.
[058] FIG. 9 is a sectional view illustrating a layered structure of a positive or negative electrode in accordance with an embodiment of the present invention.
[059] FIG. 10a is an exploded diagram illustrating a structure of a lithium ion secondary battery in accordance with an embodiment of the present invention.
[060] FIG. 10b is a diagram illustrating an external structure of a lithium ion secondary battery in accordance with an embodiment of the present invention.
[061] FIG. 11 illustrates a result of comparing the discharge rate properties measured on respective samples of a lithium ion secondary battery using a current collector according to an embodiment of the present invention and a lithium ion secondary battery using a collector of current as a comparative sample.
[062] FIG. 12 illustrates a result of comparing the charge-discharge cycle lifetimes measured on respective samples of a lithium ion secondary battery using a current collector according to an embodiment of the present invention and a lithium ion secondary battery that uses a current collector as a comparative sample.
[063] FIG. 13 illustrates a SAICAS test result comparing current collector-electrode layer adhesion intensities measured on the respective samples from a positive electrode to a secondary lithium ion battery using a current collector in accordance with an embodiment of the present invention and from a positive electrode to a secondary lithium ion battery that uses a current collector as a comparative sample. DESCRIPTION OF MODALITIES [FIRST MODALITY]
[064] As an embodiment of the present invention, a cathode sheet in which a first electrically conductive layer consisting of Ti or Al, a blended layer containing carbon and Ti or Al in a mixed state, and a second electrically conductive layer consisting of in carbon are formed into an aluminum foil with an unwrinkled surface and a solid electrolytic capacitor prepared using the cathode foil will now be described. However, as previously mentioned, each of the aluminum foil used as a substrate and Ti or Al to form the first electrically conductive layer can be replaced by another material, and the cathode sheet of the present invention has excellent properties even when a substrate surface is wrinkled as described below using performance test data. Cathode Sheet of the Present Invention
[065] Figure 1 is a sectional view illustrating a layered structure of a cathode sheet 1 according to this embodiment. The cathode sheet 1 comprises: a flat aluminum sheet 2 which is not subjected to surface wrinkling by an etching treatment or the like; a metal layer 3 formed on the flat aluminum sheet 2 and composed of a metal film consisting of Ti or Al; a blended layer 4 formed on the metal layer 3 and containing carbon and Ti or Al in a blended state; and a carbon layer 5 formed in the blended layer 4.
[066] Like flat aluminum sheet 2, it is possible to use a commercially available high purity aluminum sheet. A thickness of the aluminum sheet is not particularly limited. However, when used as a cathode sheet for a solid rolled-type electrolytic capacitor, the aluminum sheet preferably has a thickness of 20 µm to 50 µm.
[067] The metal layer 3 is formed by: placing the flat aluminum sheet 2 and a metal material of Ti or Al as a vaporization source, in a vacuum chamber; vaporization and ionization of Ti or Al, for example, by the use of electron beam and plasma generating electrodes; and introducing the positive metal ions generated into the flat aluminum sheet 2. In this process, a negative bias voltage is applied to the flat aluminum sheet 2 so that the metal ions directed to the flat aluminum sheet 2 are accelerated to have high energy (ionic metallization method). Thus, Ti or Al ions penetrate through a natural oxide film formed on the surface of the flat aluminum sheet 2 and adhere strongly to the flat aluminum sheet 2. In cases where a layer consisting of a metal's nitride or carbide, such as Ti or Al, is formed on the flat aluminum sheet 2, the first electrically conductive layer can be formed by carrying out the exposed process, for example, in an atmosphere of nitrogen gas or methane gas.
[068] Different from the ionic metallization method, as a method to form the metal layer 3, it is possible to use a vacuum vapor deposition method, a chemical vapor deposition (CVD) method or a sputter method. However, in view of an advantage of being able to allow the metal layer 3 and the flat aluminum foil 2 to strongly adhere to each other through the natural oxide film, thereby suppressing an ESR of a capacitor at a lower level , and an advantage of being able to facilitate formation of a uniform metal film, it is preferable to use the ionic metallization method.
[069] The mixed layer 4 can be formed, for example, by an ionic metallization method, as with the metal layer 3. That is, in addition to the Ti or Al metal material, a carbon material can be provided as a vaporization source to carry out a film-forming process that uses the two vaporization sources simultaneously. The introduction of the mixed layer 4 makes it possible to improve the adhesion between metal and carbon to thereby prevent the formation of an oxide film.
[070] Preferably, the mixed layer 4 is configured in such a way that, in a boundary region with the metal layer 3, it contains substantially only Ti or Al, while in a boundary region with the carbon layer 5 , it contains substantially only carbon, wherein it is particularly configured in such a way that a rate of carbon content continuously increases in a direction from the metal layer 3 to the carbon layer 5. As an example, the blended layer 4 it can be formed by: (i) during an early stage of film formation for mixed layer 4, irradiating only a metal material with an electron beam to form a film consisting only of Ti or Al; (ii) together with a lapse of time, gradually reducing an amount of electron beam irradiation to the metal material, further increasing an amount of electron beam irradiation to a carbon material, to form a mixed film containing metal and carbon in a mixed state, in which a rate of carbon content gradually increases in a direction toward a top of the deposit; and (iii) during a final stage of film formation, setting the amount of electron beam irradiation for the metal material to zero to form a film consisting only of carbon. On the other hand, when the mixed layer 4 is formed by a sputtering method, the mixed layer 4 of the preferred configuration can be formed by any suitable process, for example, together with a time course, by the gradual reduction of a voltage applied to a target metal (gradual reduction of a sputter rate of the target metal), still gradually increasing a voltage applied to a target C (gradual increase of a sputter rate of the target C).
[071] Incidentally, among the following performance test data, inventive sample data 7 to 12 are measured using a cathode sheet 1 obtained by forming a mixed layer 4 using the exposed ionic metallization method, particularly in an exposed manner such to allow a carbon content ratio to continuously increase in a direction from metal layer 3 to carbon layer 5. However, it is considered that even if mixed layer 4 partially has a region where the content ratio of carbon gradually decreases in the direction towards the carbon layer 5 (this situation may occur due to the limits of film forming techniques), it is possible to obtain excellent properties compared to a conventional cathode sheet. This is because, even in a region like this, the presence of carbon and Ti or Al in a mixed state provides better adhesion between the two component layers and therefore prevents oxidation of the Ti or Al layer to suppress generation of an internal capacitance in a cathode. Additionally, in cases where the carbon content rate changes discontinuously in a partial region of the mixed layers 4, it is considered that the ESR property is deteriorated to some degree due to an increase in interfacial resistance in the partial region. However, it is considered that the same properties of a cathode sheet can be obtained by virtue of the adhesion between the two component layers being improved by the presence of carbon and Ti or Al in a mixed state (in relation to this point, see data of inventive samples 1 to 6 between the following performance test data).
[072] The carbon layer 5 can be formed, for example, by an ionic metallization method, as with the metal layer 3 and the blended layer 4. Typically, the carbon layer 5 can be formed, after reducing the amount of electron beam irradiation to metal material to zero in the process of forming the mixed layer 4, by continuing film formation for a given time by successively irradiating only the carbon material with an electron beam.
[073] Preferably, the carbon layer 5 of the present invention is formed using an ionic or similar metallization method, rather than a method of dispersing fine carbon particles in a binder and then applying and heating the obtained mixture, as in a cathode sheet described in Patent Document 6. This is because a layer of the fine carbon particle formed using a binder comes into point contact with a lower layer of Ti or Al, causing an increase in interfacial strength and a deterioration in the adhesion between them. It is desirable to form the carbon layer 5 as a dense, uniform carbon film.
[074] It is sufficient if each of the metal layer 3, the mixed layer 4 and the carbon layer 5 has a thickness of about 0.005 to 0.01 µm. Additionally, as shown in the following performance test, at least when a total thickness of the three layers is 0.02 µm or more, good properties with respect to a cathode sheet can be obtained. However, the thickness of each of the layers can increase further.
[075] Preferably, each of the metal layer 3, the blended layer 4 and the carbon layer 5 is formed by the same film-forming method. This is because a production process can be simplified to significantly reduce production costs. However, each of the layers can be formed by a different method. Solid Electrolytic Capacitor of the Present Invention
[076] Figure 2 is an exploded diagram of a coiled-type solid electrolytic capacitor 6 prepared using the cathode sheet 1. The solid electrolytic capacitor 6 is prepared by the following method: (i) after lamination of an anode sheet 7 obtained by forming an oxide film on an anode aluminum sheet through a chemical conversion treatment, on a cathode sheet 8 with the layered structure shown in Figure 1, through a separator sheet 9, connecting an anode terminal 11 and a cathode terminal 12, respectively, on the anode sheet 7 and the cathode sheet 8, and winding the laminate to prepare a capacitor element 10; and (ii) after insertion of capacitor element 10 into an aluminum casing 13, immerse capacitor element 10 in a mixed solution comprising 3,4-ethylenedioxythiophene and p-toluenesulfonic acid and iron(II) salt as an oxidant, and which contains n-butyl alcohol as a diluent, to form a solid polyethylenedioxythiophene electrolyte layer by thermal polymerization under heat. Alternatively, the solid electrolyte layer can be formed using electrically conductive polymer based on polypyrrole or based on polyaniline or complex TCNQ salt, for example. Performance Test of the Solid Electrolytic Capacitor of the Present Invention
[077] As the cathode sheet of the present invention, a cathode sheet prepared without subjecting an aluminum sheet to surface corrugation, in the aforementioned manner, a cathode sheet prepared by intentionally subjecting an aluminum sheet to surface corrugation For comparison, a cathode sheet prepared by using a Ti layer as a metal layer and a cathode sheet prepared by using an Al layer as a metal layer were provided. Additionally, in terms of a thickness of a film consisting of a metal layer, a mixed layer and a carbon layer, each of the cathode sheets has been provided as two types: one with a thickness of 0.5 µm; and the other with a thickness of 0.02 µm. A plurality of coiled-type solid electrolytic capacitors, each with the configuration illustrated in Figure 2, were prepared using the various cathode sheets of the present invention and subjected to capacitance, ESR, and leakage current measurements. Additionally, a plurality of coiled-type solid electrolytic capacitors, each with the same configuration as the capacitors of the present invention, except that they were prepared using a plurality of conventional cathode foil types varying in varying degrees from the configuration of a substrate and a film, were subjected to the same measurement. Then both test results were compared to each other.
[078] A configuration of a cathode sheet for use in each of conventional samples 1 through 16 as solid electrolytic capacitors for comparison and inventive samples 1 through 12 as solid electrolytic capacitors of the present invention, subject to measurements, is as follows. (Conventional Sample 1)
[079] A cathode sheet obtained by subjecting a flat aluminum sheet to an etching treatment. (Conventional Sample 2)
[080] A cathode sheet obtained by forming a Ti film on a flat aluminum sheet to have a thickness of 0.5 µm. (Conventional Sample 3)
[081] A cathode sheet obtained by forming a Ti film on a flat aluminum sheet to have a thickness of 0.02 µm. (Conventional Sample 4)
[082] A cathode sheet obtained by forming a TiN film on a flat aluminum sheet to have a thickness of 0.5 µm. (Conventional Sample 5)
[083] A cathode sheet obtained by forming a TiN film on a flat aluminum sheet to have a thickness of 0.02 µm. (Conventional Sample 6)
[084] A cathode sheet obtained by forming a TiC film on a flat aluminum sheet to have a thickness of 0.5 µm. (Conventional Sample 7)
[085] A cathode sheet obtained by forming a TiC film on a flat aluminum sheet to have a thickness of 0.02 µm. (Conventional Sample 8)
[086] A cathode sheet obtained by forming a carbon film on a flat aluminum sheet to have a thickness of 0.5 µm. (Conventional Sample 9)
[087] A cathode sheet obtained by forming a carbon film on a flat aluminum sheet to have a thickness of 0.02 µm. (Conventional Sample 10)
[088] A cathode sheet obtained by forming aluminum carbide on a flat aluminum sheet and then attaching fine carbon particles onto it (a resulting film thickness varies in the range from 0.5 μm to 1 µm, depending on the positions on a surface of the cathode sheet). (Conventional Sample 11)
[089] A cathode sheet obtained by subjecting a flat aluminum sheet to an etching treatment and by forming a Ti film and a carbon film over it, in this order, to have respective thicknesses of 0.25 μm and 0.25 µm. (Conventional Sample 12)
[090] A cathode sheet obtained by subjecting a flat aluminum sheet to an etching treatment and by forming a Ti film and a carbon film over it, in this order, to have respective thicknesses of 0.01 μm and 0.01 µm. (Conventional Sample 13)
[091] A cathode sheet obtained by forming a Ti film and a carbon film on a flat aluminum sheet, in this order, to have respective thicknesses of 0.25 μm and 0.25 μm. (Conventional Sample 14)
[092] A cathode sheet obtained by forming a Ti film and a carbon film on a flat aluminum sheet, in this order, to have respective thicknesses of 0.01 μm and 0.01 μm. (Conventional Sample 15)
[093] A cathode sheet obtained by forming a film of Al on a flat aluminum sheet to have a thickness of 0.25 μm and by further forming a carbon film over it to have a thickness of 0.25 μm . (Conventional Sample 16)
[094] A cathode sheet obtained by forming a film of Al on a flat aluminum sheet to have a thickness of 0.01 μm and by additionally forming a carbon film over it to have a thickness of 0.01 μm . (Inventive Sample 1)
[095] A cathode sheet obtained by subjecting a flat aluminum sheet to an etching treatment and forming a Ti film, a mixed layer of Ti and carbon a, and a carbon film over it, in that order, to have respective thicknesses of 0.2 μm, 0.1 μm and 0.2 μm. (Inventive Sample 2)
[096] A cathode sheet obtained by subjecting a flat aluminum sheet to an etching treatment and forming a Ti film, a mixed layer of Ti and carbon a, and a carbon film over it, in that order, to have respective thicknesses of 0.008 µm, 0.004 µm and 0.008 µm. (Inventive Sample 3)
[097] A cathode sheet obtained by forming a Ti film, a mixed layer of Ti and carbon a, and a carbon film, on a flat aluminum sheet, in this order, to have respective thicknesses of 0.2 μm , 0.1 µm and 0.2 µm. (Inventive Sample 4)
[098] A cathode sheet obtained by forming a Ti film, a mixed layer of Ti and carbon a, and a carbon film, on a flat aluminum sheet, in this order, to have respective thicknesses of 0.008 μm, 0.004 µm and 0.008 µm. (Inventive Sample 5)
[099] A cathode sheet obtained by forming a film of Al, a mixed layer of Al and carbon a, and a carbon film, on a flat aluminum sheet, in this order, to have respective thicknesses of 0.2 μm , 0.1 µm and 0.2 µm. (Inventive Sample 6)
[0100] A cathode sheet obtained by forming a film of Al, a mixed layer of Al and carbon a, and a carbon film, on a flat aluminum sheet, in this order, to have respective thicknesses of 0.008 μm, 0.004 µm and 0.008 µm. (Inventive Sample 7)
[0101] A cathode sheet obtained by subjecting a flat aluminum sheet to an etching treatment and forming a Ti film, a mixed layer of Ti and carbon b, and a carbon film, over it, in this order , to have respective thicknesses of 0,2 μm, 0,1 μm and 0,2 μm. (Inventive Sample 8)
[0102] A cathode sheet obtained by subjecting a flat aluminum sheet to an etching treatment and forming a Ti film, a mixed layer of Ti and carbon b, and a carbon film, over it, in this order , to have respective thicknesses of 0.008 μm, 0.004 μm and 0.008 μm. (Inventive Sample 9)
[0103] A cathode sheet obtained by forming a Ti film, a mixed layer of Ti and carbon b, and a carbon film on a flat aluminum sheet, in this order, to have respective thicknesses of 0.2 μm, 0.1 µm and 0.2 µm. (Inventive Sample 10)
[0104] A cathode sheet obtained by forming a Ti film, a mixed layer of Ti and carbon b, and a carbon film on a flat aluminum sheet, in this order, to have respective thicknesses of 0.008 μm, 0.004 μm and 0.008 µm. (Inventive Sample 11)
[0105] A cathode sheet obtained by forming a film of Al, a mixed layer of Al and carbon b, and a carbon film on a flat aluminum sheet, in this order, to have respective thicknesses of 0.2 μm, 0.1 µm and 0.2 µm. (Inventive Sample 12)
[0106] A cathode sheet obtained by forming a film of Al, a mixed layer of Al and carbon b, and a carbon film on a flat aluminum sheet, in this order, to have respective thicknesses of 0.008 μm, 0.004 μm and 0.008 µm.
[0107] Except for the cathode sheet of the conventional sample 10, the film formation on the substrate in all the remaining samples was performed by the aforementioned ionic metallization method. Particularly, the formation of titanium nitride and titanium carbide films in conventional samples 4 to 7 was carried out in an atmosphere of nitrogen gas and methane gas, respectively, and using titanium as a vaporization source, and the formation of a carbon film in conventional samples 8 and 9 it was performed using carbon as a vaporization source. Film formation in inventive samples 1 to 12 was performed by the ionic metallization method, as previously mentioned. Among them, blended layer a in inventive samples 1 through 6 is formed to allow a ratio of carbon to Ti or Al to remain constant, while blended layer b in inventive samples 7 through 12 is formed to allow a content rate of carbon is higher in a direction facing the top of the film. In conventional sample 10, a commercially available product was used.
[0108] A performance test result is presented in the following Table 1. TABLE 1


[0109] In Table 1, “cap.”, “ESR” and “LC” mean capacitor capacitance (unit: μF), equivalent series resistance (unit: mQ) and current leakage (unit: μA), respectively. Capacitance was measured at a frequency of 120 Hz. Equivalent series resistance was measured at a frequency of 100 kHz. A value of current leakage was measured when 3 minutes elapsed after the application of a DC voltage measured at 4 V on each solid electrolytic capacitor. Respective capacitance, ESR and current leakage measurement results shown in Table 1 are illustrated graphically in figures 3 to 5.
[0110] As shown in Table 1 and the graph in Figure 3, a capacitance value measured in each of the inventive samples 1 to 12 is greater than the capacitance values measured in conventional samples 1 to 16. If compared with the measured value (175.4 μF) in conventional sample 1 which uses, as a cathode sheet, an etched sheet on which a film, such as a metal film, is not formed, the capacitance in each of the inventive samples was found to 1 to 12 increases by approximately 60%. Additionally, the capacitors in each of the conventional samples 11 and 12 and in each of the inventive samples 1, 2, 7 and 8 are different from each other only in terms of whether the mixed layer is formed between the Ti layer and the layer. of carbon in the cathode sheet (the capacitors in each of inventive samples 1 and 2 and each of inventive samples 7 and 8 are different from each other only in terms of whether a gradient is given at a content rate of each component in the mixed layer of the cathode sheet). However, it was found that the measured values (279.1 μF, 277.3 μF) in inventive samples 1 and 2 and the measured values (282.1 μF, 280.1 μF) in inventive samples 7 and 8 are greater than the measured values (264.1 μF, 258.1 μF) in the conventional samples 11 and 12. It was also found that, when compared with the measured values in the conventional samples 13 to 16, the measured values in the inventive samples 3 to 6 and 9 through 12, each again provided with the mixed layer, become larger. Particularly, it has been found that the values measured in inventive samples 7 to 12, where a gradient is given at a content rate of each component in the mixed layer in the aforementioned manner, are greater than the values measured in inventive samples 1 to 6, where no gradient is given at a content rate of each component in the blended layer.
[0111] As shown in Table 1 and the graph in Figure 4, a measured value of ESR in each of the inventive samples 1 to 12 is lower than measured values of ESR in conventional samples 1 to 16. If compared with the measured value (12.32 mQ) in conventional sample 1 which uses, as a cathode sheet, an etched sheet on which a film, such as a metal film, is not formed, it was found that the ESR in each of the inventive samples 1 to 12 is reduced by approximately 60 to 65%. Additionally, the capacitors in each of the conventional samples 11 and 12 and in each of the inventive samples 1, 2, 7 and 8 are different from each other only in terms of whether the mixed layer is formed between the Ti layer and the layer. of carbon in the cathode sheet, as previously mentioned. However, it was found that the measured values (4.76 mQ, 4.82 mQ) in inventive samples 1 and 2 and the measured values (4.61 mQ, 4.73 mQ) in inventive samples 7 and 8 are less than the measured values (6.43 mQ, 7.10 mQ) in the conventional samples 11 and 12. It was also found that, compared with the measured values in the conventional samples 13 to 16, the measured values in the inventive samples 3 to 6 and 9 through 12, each again provided with the mixed layer, become smaller. Particularly, it has been found that the values measured in inventive samples 7 to 12, where a gradient is given at a content rate of each component in the mixed layer in the aforementioned manner, are lower than the values measured in inventive samples 1 to 6, where no gradient is given at a content rate of each component in the blended layer.
[0112] Additionally, conventional samples 11 and 12 (13 and 14; 15 and 16) are an example of two capacitors that have the same film configuration on each cathode sheet and respective different film thicknesses of 0.5 μm and 0.02 µm. As shown in Table 1 and the graph in Figure 4, it was found that the ESR increases as the film thickness is reduced in each example (the increment is in the range of 0.3 mQ to 0.7 mQ). On the contrary, comparing the measured values of ESR in inventive samples 1 and 2 (3 and 4; 5 and 6) which are two different inventive samples only in film thicknesses, although the measured value (4.76 mQ) in inventive sample 1 and the measured value (4.82 mQ) in inventive sample 2 are nearly equal (such measurement results are considered to have a relationship with the wrinkling of the aluminum foil surface in inventive samples 1 and 2), the measured value ( 4.39 mQ) in inventive sample 4 is less than the measured value (4.56 mQ) in inventive sample 3, and the measured value (4.37 mQ) in inventive sample 6 is less than the measured value (4.51 mQ) in inventive sample 5. This trend is also observed in inventive samples 7 to 14, where a gradient is given to a content rate of each component in the mixed layer. Therefore, it is understood that the cathode sheet of the present invention is superior to conventional cathode sheets in that, even if a film is formed to have a relatively small thickness, the ESR property can be adequately maintained, at least in one embodiment. wherein an aluminum foil is used without being subjected to surface wrinkling.
[0113] As shown in Table 1 and the graph in Figure 5, a measured value of current leakage in each of the inventive samples 1 to 12 is smaller than the measured values of current leakage in conventional samples 1 to 16. Additionally , the values measured in inventive samples 7 to 12, each formed with the mixed layer b, are less than the values measured in the inventive samples 1 to 6, each formed with the mixed layer a. Compared to the values measured in conventional samples 11 to 16 and to the values measured in inventive samples 1 to 6, it has been found that current leakage is reduced by about 20%, based on the provision of the mixed layer. Additionally, if compared with the values measured in inventive samples 7 to 12, each provided with mixed layer b, and with the values measured in inventive samples 1 to 6, each provided with mixed layer a, it was found that the current leakage is reduced by about several %. Heat Resistance Test of the Solid Electrolytic Capacitor of the Present Invention
[0114] Next, the capacitors from the conventional samples and the capacitors from the inventive samples were subjected to a heat resistance test. The heat resistance test was carried out by applying a measured voltage of 4 V on each capacitor of conventional samples 1 to 16 and inventive samples 1 to 12, at a temperature of 125 °C for 1,000 hours, and the measured values of the capacitance and ESR before and after the test were compared.
[0115] The respective capacitance and ESR values measured after the test on each capacitor, and a rate of change of the values measured before and after the test, are shown in the following Table 2. TABLE 2

[0116] In Table 2, "Δ C/C" means a rate of change of capacitance values measured before and after testing, and a value: [(measured value after testing) - (measured value before testing)] / (value measured before the test), expressed as a percentage. Similarly, “Δ ESR/ESR” means a value of a rate of change of the measured values of the ESR before and after testing, expressed as a percentage. In the calculation for each rate of change, the value shown in Table 1 was used as the value measured before testing. Respective capacitance and ESR change rates shown in Table 2 are illustrated in graph form in figures 6 and 7.
[0117] First, in relation to a capacitance after the heat resistance test, as shown in Table 2, a capacitance value measured in each of the inventive samples 1 to 12 is greater than the capacitance values measured in conventional samples 1 to 16. Particularly, the capacitance values measured in inventive samples 7 to 12 are greater than the capacitance values measured in inventive samples 1 to 6. The capacitor of the present invention has been found to have a capacitance greater than that of the conventional capacitor even after the heat resistance test. Additionally, regarding the rate of change of capacitance values measured before and after the test, as is evident from Table 2 and Figure 6, conventional samples 1 to 16 are vastly different from inventive samples 1 to 12 in terms of rate of change. That is, in the capacitors of conventional samples 11 and 12, through the heat resistance test, the measured capacitance values are reduced by 3.8% and 4.5%, respectively. In contrast, in the capacitors of inventive samples 1 and 2, each provided with the mixed layer, the reduction rates of the measured capacitance values due to the heat resistance test are 1.6% and 2.0%, respectively. Additionally, in the capacitors from inventive samples 7 and 8, the derating rates are only 0.9% and 1.3%, respectively. Similarly, compared to the rates of reduction of capacitance values measured in conventional samples 13 to 16, the rates of reduction in inventive samples 3 to 6 and 9 to 12, each again provided with the mixed layer, are smaller, and, particularly, the reduction rates in inventive samples 9 to 12 are less than those in inventive samples 3 to 6, which show that the cathode sheet of the present invention is superior to conventional cathode sheets in the property of resisting heat relative to a capacitance property.
[0118] The capacitance reduction rates in inventive samples 7 and 8 are, respectively, 0.9% and 1.3%, while the capacitance reduction rates in inventive samples 9 and 10, in which the cathode sheet is prepared using a flat aluminum foil, are respectively 0.7% and 0.3%. That is, it can be said that, in view of the heat resistance, it is desirable to avoid subjecting an aluminum sheet to an etching treatment.
[0119] Additionally, as is evident from the graphs for inventive samples 3 through 6 and 9 through 10 of Figure 6, in these inventive samples, the rate of reduction of the measured capacitance values is suppressed at a lower level when the thickness of the film is set to 0.02 µm than when film thickness is set to 0.5 µm. That is, it can be said that, when the cathode sheet of the present invention is prepared without subjecting an aluminum sheet to an etching treatment, it is preferable to form the film so that the film has a small thickness, in view of strength. to heat.
[0120] Next, in relation to an ESR after the heat resistance test, as shown in Table 2, a measured value of the ESR in each of the inventive samples 1 to 12 is less than the measured values of the ESR in the samples conventional 1 to 16. Particularly, the measured ESR values in inventive samples 7 to 12 are smaller than the capacitance values measured in inventive samples 1 to 6. The capacitor of the present invention has been found to have an ESR lower than that of the capacitor. conventional even after the heat resistance test. Additionally, with regard to the rate of change of the ESR measured values before and after the test, as is evident from Table 2 and Figure 7, conventional samples 1 to 16 are vastly different from inventive samples 1 to 12 in terms of rate of change. That is, in the capacitors of conventional samples 11 and 12, through the heat resistance test, rates of increase of the measured values of the ESR are 18.8% and 25.4%, respectively. In contrast, in the capacitors of inventive samples 1 and 2, each provided with the mixed layer a, the rates of increase of the measured values of the ESR due to the heat resistance test are 2.5% and 2.3%, respectively. Additionally, in the capacitors of inventive samples 7 and 8, each provided with the mixed layer b, the rates of increase of the measured ESR values due to the heat resistance test are only 2.2% and 2.1%, respectively. Similarly, if compared to the rates of increase of the measured ESR values in conventional samples 13 to 16, the rates of increase in inventive samples 3 to 6 and 9 to 12, each again provided with the mixed layer, become smaller. Additionally, if compared to the rates of increase of the measured ESR values in the inventive samples 1 to 6, the rates of increase in the inventive samples 7 to 12 become smaller, which shows that the cathode sheet of the present invention is superior to the conventional cathode sheets in terms of an ESR property.
[0121] In this regard, the ESR increase rates in inventive samples 7 and 8 are, respectively, 2.2% and 2.1%, while the ESR increase rates in inventive samples 9 and 10, in which the cathode sheet is prepared using a flat aluminum sheet, are respectively 0.5% and 0.2%. That is, it can be said that, in view of the heat resistance, it is desirable to avoid subjecting an aluminum sheet to an etching treatment. [SECOND MODE]
[0122] As another embodiment of the present invention, a current collector in which a first electrically conductive layer consisting of Ti or Al, a mixed layer containing graphite-type carbon (hereinafter, occasionally referred to as "GLC") and Ti or Al in a mixed state, and a second electrically conductive layer consisting of GLC is formed from an aluminum foil with a wrinkled surface and a secondary lithium ion battery prepared using the current collector will now be described. However, as previously mentioned, each of the aluminum foil used as a substrate of the current collector and Ti or Al to form the first electrically conductive layer can be replaced by another material, and the current collector of the present invention has excellent properties even when a substrate surface is not wrinkled, as described below using performance test data. However, as previously mentioned, the application of the current collector of the present invention is not limited to a secondary lithium ion battery, but the current collector can be used for an electrode of any electrical energy storage element such as any other type of secondary battery, a double-layer electric capacitor or a hybrid capacitor. Current Collector of the Present Invention
[0123] Figure 8 is a sectional view illustrating a layered structure of a current collector 19 according to this modality. The current collector 19 comprises: a sheet metal 15 such as an aluminum foil subjected to surface wrinkling by carrying out an electrochemical etching treatment in an acidic solution; a metal layer 16 formed on the metal sheet 15 and composed of a metal film consisting of Ti or Al; a blended layer 17 formed on the metal layer 16 and which contains GLC and Ti or Al in a blended state; and a carbon layer 18 formed in the blended layer 17 and consisting of GLC.
[0124] Like aluminum foil, it is possible to use a commercially available high purity aluminum foil. A thickness of the aluminum sheet is not particularly limited. However, in view of processability, electrical conductivity, weight, volume, cost and others, aluminum foil preferably has a thickness of 5 µm to 50 µm.
[0125] The metal layer 16 is formed by: placing the metal sheet 15 and a metal material of Ti or Al, as a vaporization source, in a vacuum chamber; vaporize and ionize Ti or Al, for example, by using electron beam and plasma generating electrodes; and introducing positive metal ions generated into the metal sheet 15. An example of a film forming method includes a physical vapor deposition (PVD) method, such as an ionic metallization method. In cases where a layer consisting of nitride or carbide of a metal, such as Ti or Al, is formed on sheet metal 15, the first electrically conductive layer can be formed by carrying out the exposed process, for example, in an atmosphere of nitrogen gas or methane gas.
[0126] Unlike the ionic metallization method, a physical vapor deposition method to form the metal layer 16 includes a vacuum vapor deposition method, a sputter method, and the like. It is also possible to use a chemical vapor deposition (CVD) method, such as a thermal CVD, an optical CVD, a plasma CVD or an organic vapor phase epitaxial method.
[0127] The mixed layer 17 can be formed, for example, by an ionic metallization method, as with the metal layer 16. That is, in addition to the Ti or Al metal material, a carbon material can be provided as a vaporization source to carry out a film-forming process that uses the two vaporization sources simultaneously. The introduction of the mixed layer 17 makes it possible to improve the adhesion between the metal and the GLC to thereby prevent transformation due to a chemical reaction of the metal.
[0128] Preferably, the blended layer 17 is configured such that, in a boundary region with the metal layer 16, it contains substantially only Ti or Al, while in a boundary region with the carbon layer 18 , it contains substantially only carbon (GLC), wherein it is particularly configured in such a way that a rate of GLC content continuously increases in a direction from metal layer 16 to carbon layer 18. As an example, a mixed layer 17 can be formed by: (i) during an initial film-forming stage for mixed layer 17, irradiating only a metal material with an electron beam to form a film consisting only of Ti or Al; (ii) together with a lapse of time, gradually reducing an amount of electron beam irradiation to the metal material, further increasing an amount of electron beam irradiation to a graphite material, to form a mixed film containing metal and GLC in a mixed state, in which a rate of GLC content gradually increases in a direction toward a top of the deposit; and (iii) during a final stage of film formation, setting the amount of electron beam irradiation for the metal material to zero to form a film consisting only of GLC. On the other hand, when the mixed layer 17 is formed by a sputtering method, the mixed layer 17 of the preferred configuration can be formed by any suitable process, for example, together with a time course, by the gradual reduction of a voltage. applied to a target metal (gradual reduction of a sputter rate of the target metal), still gradually increasing a voltage applied to a target graphite (gradual increase of a sputter rate of the target graphite).
[0129] Incidentally, among the following performance test data, data from inventive samples 1 to 4 are measured using a current collector 19 obtained by forming a mixed layer 17 using the exposed ionic metallization method, particularly in an exposed manner such as to allow a GLC content rate to continuously increase in a direction from the metal layer 16 to the carbon layer 18. However, it is considered that even if the blended layer 17 partially has a region where the content rate of GLC gradually decreases in the direction towards the carbon layer 18 (this situation may occur due to the limits of film forming techniques), it is possible to obtain excellent properties compared to a conventional current collector. This is because, even in a region like this, the presence of GLC and Ti or Al in a mixed state provides better adhesion between the two components and therefore prevents transformation due to a chemical reaction such as layer oxidation. of Ti or Al, so that a contact resistance between the current collector and an electrode layer can be suppressed at a lower level for a long period of time.
[0130] The carbon layer 18 can be formed, for example, by an ionic metallization method, as with the metal layer 16 and the blended layer 17. Typically, the carbon layer 18 can be formed, after reducing the amount of electron beam irradiation for metal material to zero in the process of forming the mixed layer 17, by continuing film formation for a given time by successively irradiating only the graphite material with an electron beam.
[0131] Preferably, the carbon layer 18 of the present invention is formed using a vapor deposition method, such as an ionic plating method, as with the metal layer 16 and the blended layer 17, rather than a method of dispersing carbon particles in a binder, such as a resin binder, and then applying the obtained mixture. This is because, in a layer of carbon particles formed by kneading them together with a binder, a carbon content rate is substantially reduced by an amount corresponding to the binder, and the carbon particles come into punctual contact with a layer Ti or Al. Furthermore, in the application method, it is difficult to increase the electrical conductivity at the interface, causing an increase in interfacial resistance and a deterioration in the adhesion between them, and it is also difficult to form a thin film and uniform. It is desirable to form carbon layer 18 as a dense, uniform GLC film.
[0132] It is sufficient if each of the metal layer 16, the mixed layer 17 and the carbon layer 18 has a thickness of about 0.1 nm to 15 nm. Additionally, at least when a total thickness of the three layers is 0.3 nm or more, good properties of a current collector can be obtained. As long as electrical conductivity and economic performance are not impaired, the thickness of each of the layers can increase further. However, when the sheet metal has a corrugated surface, it is preferable that the total thickness of the three layers be set to fall within 45 nm, in view of the uniform coatability over a porous inner wall.
[0133] Preferably, each of the metal layer 16, the blended layer 17 and the carbon layer 18 is formed by the same film forming method. This is because a production process can be simplified to improve productivity and significantly reduce production costs. However, as long as economic performance is not impaired, each of the layers can be formed by a different method. Secondary Battery of the Present Invention
[0134] Figure 9 is a sectional view of a positive electrode 21 (or a negative electrode 23) prepared using the current collector 19 (the current collector used in a positive electrode and the current collector used in a negative electrode will be hereinafter referred to, respectively, as “positive side current corrector 19a” and “negative side current corrector 19b”). Figures 10a and 10b are, respectively, an exploded diagram and an appearance diagram of a lithium ion secondary battery 30 as an example of a secondary battery prepared using electrodes 21, 23. The lithium ion secondary battery 30 is prepared by the following method: (i) provide a positive electrode 21 in which an electrode layer 20 obtained by kneading lithium iron phosphate (LiFePO4) as an active substance, black acetylene as an electrically conductive auxiliary, styrene-butadiene rubber as a binder and carboxymethylcellulose ammonium salt as a thickening agent together with water are formed in current collector 19a, and a negative electrode 23 in which an electrode layer 22 obtained by kneading graphite as an active substance, black acetylene as an auxiliary electrical conductor, styrene-butadiene rubber as a binder and carboxymethylcellulose ammonium salt as a thickening agent together with water are formed n the current collector 19b; and laminating the positive electrode 21 to the negative electrode 23 through a separator, after which a positive plate terminal 26 and a negative plate terminal 27 are respectively connected to the positive side current collector 19a and the current collector on the negative side 19b, and a plurality of laminates are stacked to prepare a battery element 28; and (ii) after insertion of the battery element 28 into a housing 29, injecting, into the housing, an electrolyte solution obtained by dissolving lithium hexafluorophosphate (LiPF6) as an electrolyte 25 in a mixed solution of ethylene carbonate and carbonate diethyl as organic solvents and then sealing the casing. It is understood that respective materials of active substance, electrically conductive auxiliary, binder and electrolyte solution, a combination of these, and an element structure (coin type, rolled type or stacked type) are not limited to the above example. Performance Test of the Current Collector of the Present Invention
[0135] A performance test of the current collector of the present invention was carried out for a current collector prepared using, as a substrate, an aluminum foil subject to surface wrinkling by performing an electrochemical etching treatment in an acidic solution, in the aforementioned manner, and a current collector prepared using, as a substrate, an aluminum foil which is not subject to surface wrinkling. On each of the current collectors, a Ti or Al layer was used as the metal layer, and a total thickness of the metal layer, mixed layer and carbon layer was set to 25 nm. In order to improve the accuracy of the assessment, a performance test coin battery was prepared as a secondary lithium ion battery element for performance assessment by using a layered electrode as a positive electrode. of exposed electrode formed in the current collector, and by the use of a lithium plate as a counter electrode. By using the coin-type battery, a positive electrode discharge rate property and a charge-discharge cycle lifetime property were measured and evaluated.
[0136] The property of the positive electrode discharge rate was evaluated by: performing (i) a charge operation to charge the coin-type battery to 4.2 V at a given charge rate (charge current value) at a constant current charge mode and then charge the coin battery in a constant voltage charge mode until the charge current value becomes 0.01 C, once and then performing (ii ) a discharge operation to discharge the coin-type battery up to 3.0 V at a particular discharge rate (discharge current value) in a constant current discharge mode, once; and calculating a capacity maintenance ratio (“discharge capacity [mAh/g] at each discharge rate (discharge current value)” / “discharge capacity [mAh/g] at a discharge rate (value of discharge current) of 0.2 C" x 100), from a coin-type battery discharge capacity ratio measured at each discharge rate (discharge current value) based on a discharged capacity at a rate of discharge (discharge current value) of 0.2 C. The discharge rate property was evaluated by setting an ambient temperature at 25 °C and changing the discharge rate (discharge current value) in the range of 0 .2 C to 10 C, and the ratios of capacity maintenance at the respective discharge rates (discharge current values) were compared with each other. When the discharge rate (discharge current value) is less than 1 C, the given charge rate (charge current value) has been set to the same value as the discharge rate (discharge current value). When the discharge rate (discharge current value) is equal to or greater than 1 C, the given charge rate (charge current value) has been fixed at 1 C. In this particular, a discharge rate (value of the current of discharge) 1 C represents a current value to discharge the full capacity of a battery in one hour and a discharge rate (discharge current value) 10 C represents a current value to quickly discharge the full capacity of a battery in 6 minutes.
[0137] The lifetime characteristic of the charge cycle - discharge of the positive electrode was evaluated by: setting an ambient temperature at 25 °C; setting each of the charge rate (charge current value) and discharge rate (discharge current value) to 1 C; repetition of charge-discharge cycle exposed 20 times; and calculating a capacity maintenance ratio based on an initial discharge capacity (in the first cycle) each time a cycle is completed.
[0138] In order to verify an effect of sheet metal surface wrinkling in relation to the strength of adhesion between the current collector and the electrode layer, a test was performed using a SAICAS (Surface Cut Analysis System E Interfacial) as an oblique cutting device. A cutting blade with a diamond cutting edge with a width of 1 mm was cut in the battery from an electrode surface at a constant speed (horizontal component: 6 µm/s, vertical component: 0.6 µm/sec ). After reaching a joint interface between the current collector and the electrode layer, a horizontal voltage imposed on the cutting blade during the horizontal movement of the cutting blade at a constant speed (horizontal component: 6 μm/s) was measured and compared as a stripping resistance.
[0139] A configuration of a current collector for use in each of comparative samples 1 through 7 as secondary batteries for comparison and inventive samples 1 through 4 as secondary batteries of the present invention, subject to measurements, is as follows. (Comparative Sample 1)
[0140] A current collector composed of a flat aluminum sheet. (Comparative Sample 2)
[0141] A current collector obtained by subjecting a flat aluminum sheet to an etching treatment. (Comparative Sample 3)
[0142] A current collector obtained by forming a graphite-like carbon film to have a thickness of 20 nm on a flat aluminum sheet. (Comparative Sample 4)
[0143] A current collector obtained by forming a Ti film to have a thickness of 12.5 nm on a flat aluminum sheet, and by forming a graphite-like carbon film on it to have a thickness of 12.5 nm. (Comparative Sample 5)
[0144] A current collector obtained by subjecting a flat aluminum sheet to an etching treatment and by forming a Ti film and a graphite-like carbon film in this, in this order, to have respective thicknesses of 12.5 nm and 12.5 nm. (Comparative Sample 6)
[0145] A current collector obtained by forming a film of Al to have a thickness of 12.5 nm on a flat aluminum sheet, and by forming a graphite-like carbon film on it to have a thickness of 12.5 nm. (Comparative Sample 7)
[0146] A current collector obtained by subjecting a flat aluminum sheet to an etching treatment and by forming an Al film and a graphite-like carbon film in this, in this order, to have respective thicknesses of 12.5 nm and 12.5 nm. (Inventive Sample 1)
[0147] A current collector obtained by forming a Ti film, a mixed layer of Ti and graphite-like carbon and a graphite-like carbon film on a flat aluminum sheet, in this order, to have respective thicknesses of 10 nm, 5 nm and 10 nm. (Inventive Sample 2)
[0148] A current collector obtained by subjecting a flat aluminum sheet to an etching treatment and by forming a Ti film, a mixed layer of Ti and graphite-like carbon and a graphite-like carbon film in this, in that order , to have respective thicknesses of 10 nm, 5 nm and 10 nm. (Inventive Sample 3)
[0149] A current collector obtained by forming an Al film, a mixed layer of Al and graphite-like carbon and a graphite-like carbon film on a flat aluminum sheet, in this order, to have respective thicknesses of 10 nm, 5 nm and 10 nm. (Inventive Sample 4)
[0150] A current collector obtained by subjecting a flat aluminum sheet to an etching treatment and by forming an Al film, a mixed layer of Al and graphite-like carbon and a graphite-like carbon film in this, in this order , to have respective thicknesses of 10 nm, 5 nm and 10 nm.
[0151] In this particular, the film formation on the metal sheet in all samples was performed by the aforementioned ionic metallization method.
[0152] Test results on the property of the discharge rate for the comparative and inventive samples are presented in the following Tables 3 through 13. Additionally, the capacity maintenance ratio determined at each discharge rate (discharge current value) is illustrated in the graphic form of figure 11. TABLE 3




[0153] As seen in Figure 11, it is apparent that the inventive samples 1 to 4, each using the current collector of the present invention, are improved in the property of the discharge rate, compared to the current collectors of the comparative samples 1 to 7.
[0154] Additionally, the capacity maintenance ratios determined as test results on the lifetime property of the charge-discharge cycle, every time a charge-discharge cycle in each of comparative samples 1 to 7 and samples inventions 1 to 4 is completed, are presented in the following Tables 14 and 15 and additionally illustrated in the form of the graphic in Figure 12. TABLE 14


[0155] In Figure 12, compared to the lifetime property of the charge cycle - battery discharge using the current collectors of comparative samples 1 to 7, in which a reduction in the capacity maintenance ratio occurs along with a increase in the number of cycles, in any of the inventive samples 1 to 4, each using the current collector of the present invention, no reduction in capacity occurs before 20 cycles, which clearly shows the improvement in the cycle lifetime property loading - unloading.
[0156] A SAICAS test result to evaluate the effect of wrinkling the surface of the sheet metal in relation to the strength of adhesion between the current collector and the electrode layer, for comparative samples 1 and 2 and inventive samples 1 and 2, is illustrated in Figure 13. It is evident that the effect of wrinkling the surface of the sheet metal in relation to the strength of adhesion with the electrode layer is present, irrespective of the presence or absence of a film.
[0157] As stated, it has been found that an electrode prepared using the current collector of the present invention exhibits significantly small deterioration in quality due to use at a high rate of discharge and a large number of repetitive uses. Such an effect is believed to be created based on the high electrical conductivity and chemical stability at the interface achieved by the previously mentioned film configuration of the current collector of the present invention. It is evident that the improvement in electrical conductivity and chemical stability arising from the film configuration of the present invention does not depend on a specific current collector application. In view of this, it is considered that when the current collector of the present invention is used in a negative electrode of a secondary lithium ion battery or in a positive or negative electrode of a double-layer electric capacitor or a hybrid capacitor , quality deterioration can be suppressed in the same way. INDUSTRIAL APPLICABILITY
[0158] The electrode material of the present invention can be used as a cathode sheet of a solid rolled-type or stacked-type electrolytic capacitor. The electrode material of the present invention is also usable in various capacitors, including an electrolytic capacitor which operates using an electrolytic solution, an electric double layer capacitor, a lithium ion capacitor, a lithium ion battery, a solar battery, and others.
[0159] The current collector of the present invention can be used as an electrode of a secondary battery, a double-layer electrical capacitor or a hybrid capacitor. The current collector of the present invention is also usable in a solar battery or the like that is powered using an electrolyte. EXPLANATION OF THE CODES 1: cathode sheet 2: flat aluminum sheet 3: metal layer 4: mixed layer 5: carbon layer 6: rolled-type solid electrolytic capacitor 7: anode sheet 8: cathode sheet 9: separator sheet 10 : capacitor element 11: anode terminal 12: cathode terminal 13: aluminum casing 14: rubber seal 15: metal sheet 16: metal layer 17: mixed layer 18: carbon layer 19: current collector (19a: current collector on the positive side, 19b: current collector on the negative side) 20: positive electrode layer 21: positive electrode 22: negative electrode layer 23: positive electrode 24: separator 25: electrolyte 26: positive terminal 27: negative terminal 28: secondary lithium ion battery element 29: battery case 30: secondary lithium ion battery

权利要求:
Claims (19)
[0001]
1. Electrode material (1), characterized in that it is constructed by forming, on an electrode substrate (2), a first electrically conductive layer (3) that contains a metal, a mixed layer (4) that contains carbon and a substance that makes up the first electrically conductive layer that contains a metal in a mixed state, and a second electrically conductive layer (5) consisting of carbon, wherein the mixed layer (4) is configured to have a changing composition. from a state that contains only the substance that makes up the first electrically conductive layer (3) that contains a metal to a state that contains only carbon, in a direction from the first electrically conductive layer (3) that contains a metal to the second conductive layer electrically (5), wherein the mixed layer (4) includes a portion that continuously changes in a direction from the first electrically conductive layer (3) containing a metal to the second electrically conductive layer (5).
[0002]
2. Electrode material (1) according to claim 1, characterized in that the first electrically conductive layer (3) containing a metal contains at least one element selected from the group consisting of Ta, Ti, Cr, Al, Nb, V, W, Hf, Cu, nitrides of these metals and carbides of these metals.
[0003]
3. Electrode material (1) according to claim 1 or 2, characterized in that the electrode substrate (2) has an unwrinkled surface.
[0004]
4. Solid electrolytic capacitor (6) comprising an anode sheet (7), a cathode sheet (1, 8), a separator (9) provided between the anode (7) and cathode sheets (1, 8) , and a solid electrolyte layer formed between the anode (7) and cathode (1, 8) sheets, characterized in that the solid electrolytic capacitor (6) comprises the electrode material (1) as defined in either of claims 1 to 3 which is used as the cathode sheet (8).
[0005]
5. Solid electrolytic capacitor (6), according to claim 4, characterized in that the solid electrolyte layer contains at least one element selected from the group consisting of manganese dioxide (MnO2), tetracyanoquinodimethane (TCNQ) , polyethylenedioxythiophene (PEDOT), polyaniline (PANI) and polypyrrole.
[0006]
6. Cathode sheet (1, 8) for use in a solid electrolytic capacitor (6) with a capacitor element (10) comprising an anode sheet (7), a cathode sheet (1, 8), a separator ( 9) provided between the anode (7) and cathode (1, 8) sheets, and a layer of solid electrically conductive polymer formed between the anode (7) and cathode (1, 8) sheets, characterized in that that the cathode sheet (1, 8) comprises: an aluminum sheet (2) with an unwrinkled surface; a metal layer (3) formed on the aluminum sheet (2) and consisting of Ti or Al; a blended layer (4) formed on the metal layer (3) and containing carbon and Ti or Al in a blended state; and a carbon layer (5) formed in the blended layer (4) and consisting of carbon, wherein the blended layer (4) is configured to have a composition that changes from a state containing only Ti or Al to a state that contains only carbon, in one direction from the metal layer (3) to the carbon layer (5), wherein the blended layer (4) includes a portion that continuously changes in one direction from the metal layer (3) to the carbon layer (5).
[0007]
7. Current collector (19, 19a, 19b) for an electrode (21, 23), characterized in that it is constructed by forming, on a substrate (15) containing a metal, a first electrically conductive layer (16 ) which contains a metal, a mixed layer (17) that contains carbon and a substance that makes up the first electrically conductive layer (16) which contains a metal in a mixed state, and a second electrically conductive layer (18) which consists of carbon , wherein the mixed layer (17) is configured to have a composition that changes from a state containing only the substance that makes up the first electrically conductive layer containing a metal to a state containing only carbon, in a direction of the first layer electrically conductive (16) containing a metal to the second electrically conductive layer (18), wherein the blended layer (17) includes a portion that continuously changes in a direction from the first electrically conductive layer (16) containing a metal to the second conductive layer and electrical (18).
[0008]
8. Current collector (19, 19a, 19b), according to claim 7, characterized in that the first electrically conductive layer (16) containing a metal contains at least one element selected from the group consisting of Ta, Ti, Cr, Al, Nb, V, W, Hf, Cu, nitrides of these metals and carbides of these metals.
[0009]
9. Current collector (19, 19a, 19b), according to claim 7 or 8, characterized in that the carbon is graphite-type carbon.
[0010]
10. Current collector (19, 19a, 19b) according to any one of claims 7 to 9, characterized in that the substrate (15) containing a metal is a sheet metal consisting of at least one element selected from the group consisting of aluminum or aluminum alloy, Ti, Cu, Ni, Hf and stainless steel.
[0011]
11. Current collector (19, 19a, 19b) according to any one of claims 7 to 10, characterized in that the substrate (15) containing a metal has a wrinkled surface.
[0012]
12. Positive electrode (21) for a non-aqueous electrolytic secondary battery (30), wherein an electrode layer (20) is formed on the current collector (19, 19a) as defined in any one of claims 7 to 11, characterized in that the electrode layer (20) comprises: an active substance that includes a transition metal oxide or transition metal phosphate compound that contains an alkali metal or an alkaline earth metal; an auxiliary electrical conductor; and a binder.
[0013]
13. Negative electrode (23) for a non-aqueous electrolytic secondary battery (30), wherein an electrode layer (22) is formed on the current collector (19, 19b) as defined in any one of claims 7 to 11, characterized in by the fact that the electrode layer (22) comprises: an active substance that includes at least one element selected from the group consisting of a carbon material capable of blocking and releasing an alkali metal ion or alkali metal ion- earth, Sn, Si or silicon oxide, S or sulfide, and titanium oxide; an auxiliary electrical conductor; and a binder.
[0014]
14. Non-aqueous electrolytic secondary battery (30), characterized in that it uses at least one of the positive electrode (21) as defined in claim 12 and the negative electrode (23) as defined in claim 13.
[0015]
15. Electrode (21, 23) for a non-aqueous electrolytic double layer electrical capacitor, wherein an electrode layer (20, 22) is formed on the current collector (19, 19a, 19b) as defined in any one of the claims 7 to 11, characterized in that the electrode layer (20, 22) comprises: an active substance that includes activated carbon or carbon nanotube; an auxiliary electrical conductor; and a binder.
[0016]
16. Non-aqueous electrolytic double layer electrical capacitor comprising a positive electrode (21) and a negative electrode (23), characterized in that the electrode (21, 23) as defined in claim 15 is used as at least one of the positive (21) and negative (23) electrodes.
[0017]
17. Positive electrode (21) for a non-aqueous hybrid electrolytic capacitor, in which an electrode layer (20) is formed in the current collector (19a) as defined in any one of claims 7 to 11, characterized in that the electrode layer (20) comprises: an active substance that includes activated carbon or carbon nanotube; an auxiliary electrical conductor; and a binder.
[0018]
18. Negative electrode (23) for a non-aqueous hybrid electrolytic capacitor, wherein an electrode layer (22) is formed on the current collector (19b) as defined in any one of claims 7 to 11, characterized in that the electrode layer (22) comprises: an active substance that includes at least one element selected from the group consisting of a carbon material capable of blocking and releasing an alkali metal ion or alkaline earth metal ion, Sn, Si or silicon oxide, S or sulfide, and titanium oxide; an auxiliary electrical conductor; and a binder.
[0019]
19. Non-aqueous hybrid electrolytic capacitor, characterized in that it uses at least one of the positive electrode (21) as defined in claim 17 and the negative electrode (23) as defined in claim 18.

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CA2827919A1|2012-08-30|

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CN107403697B|2018-11-09|

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BR112013021247A2|2020-06-30|

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AU2016277576B2|2018-01-25|

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法律状态:
2020-07-14| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-09-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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