JP5519188B2 - Lithium secondary battery or capacitor - Google Patents

Description

  The present invention relates to lithium secondary batteries and capacitors such as lithium ion batteries and lithium polymer batteries.

  Lithium secondary batteries have been ignited in the past by electrical appliances caused by batteries, and are being developed to ensure safety. However, in recent years, a fake battery (hereinafter referred to as a “counterfeit”) has come to the market as if it were a genuine product of a manufacturer. Many counterfeit products only show a certain level of performance as a battery and are not adequately quality controlled.If used, there is a risk of destroying electrical products. In the worst case, fire, burns, blindness, etc. May cause serious accidents affecting human body. Capacitors have the same problem, and it is necessary to easily distinguish between genuine products and counterfeit products in order to increase the reliability of lithium secondary batteries and capacitors. Therefore, the advent of lithium secondary batteries and capacitors that can be easily identified as genuine and difficult to manufacture counterfeit products is desired.

  In addition, an identification method (Patent Document 1) of an article that has a simple configuration and is difficult to counterfeit, an authentication method and an apparatus (Patent Document 2) that can ensure reliability are provided. However, there is no description about the problem that the lithium secondary battery and the capacitor have, and there is, of course, no example in which these identification method and authentication method and apparatus are applied to the authentication of the lithium secondary battery and capacitor.

JP 2008-96159 A WO2005 / 055154

  The problem to be solved by the present invention is to provide a lithium secondary battery and a capacitor that can easily determine whether or not they are genuine products and that make it difficult to produce counterfeit products.

According to the present invention, as a means for solving the above-mentioned problem, it is a group of one or more elements that emit specific fluorescence upon irradiation with electromagnetic waves in a specific wavelength region, and the spectral distribution shape of the emitted fluorescence. The material with specific information is attached to the base material layer consisting of a biaxially stretched polyester film and a biaxially stretched nylon film of an outer packaging material in which a base material layer, a barrier layer, and a sealant layer are sequentially laminated. Provided is a lithium secondary battery or a capacitor characterized in that the lithium secondary battery or the capacitor is included in an adhesive layer for bonding, or an adhesive for laminating a base material layer and a barrier layer.

A step of associating specific information with a spectral distribution shape of fluorescence emitted by a substance that is a group of one or more elements that emit fluorescence specific to electromagnetic wave irradiation in a specific wavelength region, using the substance Producing the lithium secondary battery or capacitor, and recognizing information associated with the spectral distribution shape of fluorescence obtained by irradiating the lithium secondary battery or capacitor with electromagnetic waves in a specific wavelength region. A feature of a method for identifying a lithium secondary battery or capacitor is provided.

The lithium secondary battery or capacitor of the present invention is a group of one or more elements that emit specific fluorescence upon irradiation with electromagnetic waves in a specific wavelength region, and is specific to the spectral distribution shape of the emitted fluorescence. The exterior material includes a substance associated with information (hereinafter referred to as an information presentation substance). Therefore, when the lithium secondary battery or capacitor of the present invention is irradiated with electromagnetic waves in a specific wavelength region, specific fluorescence is emitted. By measuring the spectral distribution of the fluorescence, information associated with the spectral distribution shape can be recognized. Therefore, if the manufacturer's name of the battery or capacitor is associated with the spectral distribution shape of the fluorescence emitted from the information-presenting substance in advance, the battery or capacitor is irradiated with electromagnetic waves, and the emitted fluorescent spectrum distribution is simply measured. Thus, the manufacturer of the battery or capacitor can be recognized, and it can be known that it is a genuine product. Therefore, when a counterfeit product appears, it can be eliminated, and an accident caused by the counterfeit product can be prevented.
In addition, the shape of the spectral distribution of the fluorescence emitted by the information-presenting substance changes when the combination of elements and the mixing ratio change, so a third party who is not familiar with the relationship between the element and the fluorescence spectrum has the same spectral distribution as the information-presenting substance. It is difficult to produce a material exhibiting Therefore, it is very difficult to make a counterfeit product for the battery or capacitor of the present invention.

  The lithium secondary battery or capacitor of the present invention contains an information presenting substance in the exterior material. The information presenting substance is a group of one or more elements that emit specific fluorescence upon irradiation with electromagnetic waves in a specific wavelength region (for example, ultraviolet rays in a predetermined wavelength region), and has a spectral shape of the emitted fluorescence. It is a substance with specific information associated with it. The fluorescence emitted from the information presenting substance is emitted when the information presenting substance is excited from the ground level to the higher energy level by the external electromagnetic wave irradiation and then transitions to the lower energy level.

As the information presenting substance, an element which is not generally contained in the battery or the outer packaging material of the capacitor is suitable, and specifically, an element having atomic number 31 to atomic number 88 is suitable. Among them, lanthanoid elements, particularly transition elements having incomplete 4f orbits such as cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), Terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb) are suitable. These elements can be easily identified from the spectral distribution, are economical and hygienic, and are easily available as oxides.
These elements may be used alone to form an information presentation material, but two or more types may be combined to form an information presentation material. Even if the information presenting substance contains the same element, the shape of the spectrum distribution of the emitted fluorescence will be different if the type of other elements to be combined and the ratio of the combination are different. be able to.
Further, the information presenting substance described above may be used as it is, but may be used as a compound (oxide, sulfide, organic complex).

Further, the information presenting substance may be contained in a predetermined base substance such as yttrium oxide containing europium. The base material includes oxides, sulfides, nitrides, hydroxides, halides, mixed crystals, amorphous materials, and glass. For example, those containing the above-mentioned elements in the form of chemical bonds such as chelate compounds, those substituted with other atoms or ions constituting the crystal lattice, those included by being inserted into the crystal lattice, or glass What is contained in the gap in the inside.
In particular, when the information presenting substance is made of an inorganic oxide as a base material and added with the above-described elements, the information presenting substance becomes very stable and is not destroyed even at a high temperature of 1000 ° C. Therefore, if such a substance is used as an information presentation substance, the information presentation substance remains undestructed even if the lithium secondary battery or capacitor does not remain in its original state due to a fire accident, etc. Thus, the information associated with the information presenting substance can be recognized.

  In the present invention, it is necessary to include the information presenting substance in an exterior material. The packaging material is not particularly limited as long as it satisfies the performance required as a packaging material for a lithium secondary battery or a capacitor, and further contains an information presenting substance in at least one layer. In general, a base material layer, a barrier layer, a sealant The layer is the basic structure.

The base material layer is a layer that provides strength and insulation to the exterior material. Specifically, a biaxially stretched polyester film or a biaxially stretched nylon film is suitable, and in particular, a biaxially stretched polyester film and a biaxially stretched nylon film. A two-layer film in which is laminated is suitable. In this case, since the nylon resin is altered when the electrolytic solution adheres, the layer in contact with the metal foil of the base material layer is a biaxially stretched nylon film, and the layer that is the outermost layer of the base material layer is a biaxially stretched polyester. A film is preferred. Although the specific manufacturing method of a biaxially stretched film is not specifically limited, for example, after forming a polyester resin or a nylon resin into a film shape by using a T-die extrusion method, the film is stretched in two directions in the vertical and horizontal directions using a tenter stretching machine. And a method of stretching and producing in two longitudinal and lateral directions while forming a film using an inflation extrusion molding method.
The biaxially stretched polyester film is formed from a resin such as a copolymer polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene terephthalate / ethylene isophthalate copolymer or butylene terephthalate / butylene isophthalate copolymer. The biaxially stretched nylon film is made of a resin such as nylon 6, nylon 6,6, a copolymer of nylon 6,6 and nylon 6, nylon 6,10, polymetaxylylene adipamide (MXD6), etc. Can be molded from

  The barrier layer is a layer for preventing water vapor from entering the battery from the outside. As the barrier layer, a metal foil such as aluminum, nickel, and stainless steel may be used, but it is preferable to use an aluminum foil in consideration of economy. In addition, it is known that aluminum foil contains a slight amount of iron to improve the spreadability and to reduce the occurrence of pinholes due to bending. Therefore, when an aluminum foil is used as the barrier layer, it is preferable to use one containing 0.3 to 9.0% by weight, preferably 0.7 to 2.0% by weight of iron. In addition, the aluminum foil produced by cold rolling changes its flexibility, waist strength, and hardness under annealing (so-called annealing treatment) conditions. However, when aluminum foil is used in the present invention, it is annealed. It is better to have a soft tendency to be annealed somewhat or completely than a hard-treated product.

  Moreover, the surface of metal foil (particularly aluminum foil) is easily dissolved and corroded by an acidic substance or the like. Therefore, it is desirable to perform acid resistance treatment on the barrier layer. When acid-resistant treatment is performed, even if acidic substances such as hydrofluoric acid are generated from the inside of the battery, etc., the barrier layer surface is prevented from dissolving and corroding, and pinholes are prevented from being generated in the barrier layer. . Furthermore, the acid resistance treatment also has the effect of improving the adhesion between the barrier layer and the sealant layer. As an acid-resistant treatment method, chromate treatment is generally used, but non-chromate treatment such as boehmite treatment, parkerizing treatment, triazine thiol treatment, and the like are also possible. Moreover, although the acid-resistant treatment may be performed only on the surface of the barrier layer on the sealant layer side, it may be performed on both surfaces.

Next, the sealant layer will be described. The sealant layer is made of polyethylene resin such as low density polyethylene, high density polyethylene, and ethylene-α olefin copolymer, polypropylene resin such as polypropylene and propylene / ethylene copolymer, and these resins are mixed with unsaturated carboxylic acid or acrylic resin. It is formed from a resin modified with acid, methacrylic acid, maleic anhydride, or the like, or an ion-crosslinked resin.
The sealant layer was modified with a layer made of unmodified polyethylene resin or polypropylene resin (hereinafter referred to as an unmodified resin layer), and unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic anhydride, or the like. It may be a two-layer made of a polyethylene resin or a polypropylene resin (hereinafter referred to as a modified resin layer). The exterior material in which the sealant layer is composed of two layers, a modified resin layer and an unmodified resin layer, and the base material layer / barrier layer / modified resin layer / non-modified resin layer are laminated in order, has an adhesive force between the barrier layer and the sealant layer. In addition, the heat sealability is also excellent.

  The method for bonding the base material layer, the barrier layer, and the sealant layer is not particularly limited. For example, the base material layer is first bonded to one side of the barrier layer with an adhesive, and then to the other side of the barrier layer. The sealant layer may be bonded by thermocompression bonding.

  Although there is no particular limitation on the method of including the information presenting substance in these outer packaging materials, as described above, since the metal foil is suitably used for the barrier layer, the information presenting substance is arranged in the barrier layer and the sealant layer. Then, since the electromagnetic wave does not pass through the metal foil, the electromagnetic wave may not reach the information presenting substance unless the battery or the capacitor is destroyed. Therefore, in order to specify the information presenting substance in a non-destructive manner, the information presenting substance must be disposed outside the barrier layer. For this purpose, (1) the information presentation substance is added to an adhesive for bonding the base material layer and the barrier layer, or (2) the information presentation substance is arranged in the base material layer, or (3) A dispersion liquid containing the information presenting substance may be printed on the base material layer.

  In addition, (2) In order to include the information presenting substance in the base material layer, the information presenting substance may be kneaded in advance in the resin constituting the base material layer, but the base material layer is biaxially stretched with the biaxially stretched polyester film. When it is a laminated film with a nylon film, it may be added to an adhesive layer for bonding them together.

  (3) In order to print a dispersion liquid containing an information presenting substance on a base material layer, for example, the information presenting substance is dispersed in a binder component such as acrylic, acrylurethane or acrylamide, and this is subjected to gravure printing. Or by inkjet printing. The printing may be performed on the entire surface of the base material layer, may be performed on a part of the base material layer, and may be performed in the form of characters, figures, barcodes, and the like. Using an information presentation substance that emits fluorescence in the visible light region and printing it in the form of letters, diagrams, barcodes, etc., by irradiating the battery or capacitor with electromagnetic waves in a specific wavelength region, It can also be raised.

  In addition, when manufacturing the exterior material containing a different information presentation substance little by little, (3) The method of printing an information presentation substance on a base material layer is suitable. A wide variety of exterior materials can be efficiently manufactured by manufacturing a large amount of exterior materials in advance and then printing different information-presenting substances in small amounts. Further, when printing the information presentation material, the information presentation material may be peeled off due to friction or the like. Therefore, (3) when the information presentation substance is printed on the base material layer, it is desirable to further provide a protective layer such as a hard coat layer for the purpose of protecting the printing layer containing the information presentation substance. The protective layer can be provided by printing again only the binder component of the printing layer.

  The lithium secondary battery is formed by forming the above-described exterior material into a bag shape or a tray shape, a positive electrode material composed of a positive electrode current collector and a positive electrode active material layer, a polymer electrolyte layer infiltrated with an electrolytic solution, a negative electrode current collector and a negative electrode active material. Insert the battery body laminated with the negative electrode material consisting of the material layer, then insert the positive electrode lead and negative electrode lead into the container so that one end is each electrode material and the other end is outside the container, and finally the container is sealed It is good to manufacture. Alternatively, a positive electrode material, a separator, and a negative electrode material may be laminated, inserted into a container, filled with an electrolytic solution, and finally, the positive electrode lead and the negative electrode lead may be inserted and the container sealed. In addition, the capacitor is formed by stacking the above-described exterior material into a bag shape or a tray shape, and sandwiching an activated carbon electrode and a separator infiltrated with an electrolyte between aluminum current collector plates, and one end of the current collector plate outside the container. It is good to manufacture by enclosing while projecting.

The information indicated by the spectral distribution shape of the fluorescence emitted by the information-presenting substance is not particularly limited as long as it includes information required by the battery and capacitor, such as the name of the manufacturing factory and the name of the electrical product to be incorporated. If you associate the manufacturer name of the capacitor and capacitor, it is easy to understand that it is a genuine product.
Also, means for storing information such as the spectrum distribution shape emitted by the information presenting substance and the manufacturer name associated therewith, means for extracting the spectrum distribution from the information presenting substance such as an electromagnetic wave irradiating apparatus or a fluorescence spectrum detector, and the like Using an “information management device” that also has a means for querying and outputting information such as the manufacturer name from the shape of the extracted spectrum distribution, the manufacturer name, etc. can be obtained simply by supplying a battery or capacitor to the device. Information can be extracted, and genuine products can be determined.
Note that γ rays, X rays, ultraviolet rays, and the like can be used as the electromagnetic waves. Specifically, ultraviolet light having a specific wavelength can be exemplified, and examples of the light source for irradiating ultraviolet light include a mercury lamp and a metal halide lamp.

Next, the present invention will be described with reference to examples, but the present invention is not limited thereto.
First, an exterior material that does not contain an information presentation substance is manufactured. First, a biaxially stretched nylon film and a biaxially stretched polyester film are bonded together via an adhesive to obtain a base material layer. Next, chromate treatment is performed on one surface of the aluminum foil, and this is used as a barrier layer. In addition, a two-layer film having a maleic anhydride-modified polypropylene layer and a propylene / ethylene copolymer layer is produced and used as a sealant layer.
Subsequently, a base material layer, a barrier layer, and a sealant layer are bonded together. The base material layer and the barrier layer were attached using an adhesive so that the biaxially stretched nylon film layer of the base material layer and the surface of the barrier layer not subjected to the chromate treatment were in contact with each other. The barrier layer and the sealant layer were bonded together by thermocompression bonding without using an adhesive, and bonded so that the chromate-treated surface of the barrier layer was in contact with the maleic anhydride-modified polypropylene layer.

  Next, a group of elements that emit specific fluorescence upon irradiation with electromagnetic waves in a specific wavelength region, and a substance (information presentation) associated with the information “○ × company” to the spectrum distribution shape of the emitted fluorescence Material) is dispersed in a binder to prepare a dispersion. This dispersion was printed on the entire surface of the base material layer of the exterior material with a gravure printing machine. Further, the exterior material was formed into a bag shape, and the battery body was inserted to manufacture the lithium secondary battery of the present invention.

  Next, information is taken out from the battery. For information extraction, an information management apparatus was used in which the information “Ox company” was stored with respect to the spectral distribution shape of the fluorescence emitted from the information presenting substance. When the lithium secondary battery is provided to the information management device, the information management device irradiates the lithium secondary battery with an electromagnetic wave in a specific wavelength region, and fluorescence is emitted from the information presenting substance that receives the electromagnetic wave. Further, the information management device analyzed the spectrum distribution shape of the emitted fluorescence, and information “○ × company” was obtained.

Since the lithium secondary battery or capacitor of the present invention can be determined to be a genuine product, it can be easily removed when a counterfeit product appears, and can be used to prevent accidents caused by the counterfeit product. . Even if a blast accident occurs, it can be determined whether or not a genuine battery was used from the battery exterior material after the accident, so that it can be used to investigate the cause of the accident.
Furthermore, by associating information such as the date of manufacture, manufacturing factory, and manufacturing lot with the information presenting substance, it is possible to identify the attributes of the product.

Claims (2)

A substance that is a group of one or more elements that emit specific fluorescence in response to electromagnetic wave irradiation in a specific wavelength region, and that has specific information associated with the spectral distribution shape of the emitted fluorescence,
Adhesive layer or base material layer for laminating a base material layer composed of a biaxially stretched polyester film and a biaxially stretched nylon film of an exterior material in which a base material layer, a barrier layer, and a sealant layer are sequentially laminated A lithium secondary battery or a capacitor, which is contained in an adhesive disposed between the electrode and the barrier layer. Associating specific information with the spectral distribution shape of fluorescence emitted by a substance that is a group of one or more elements that emit fluorescence specific to electromagnetic wave irradiation in a specific wavelength region;
The step of producing a lithium secondary battery or capacitor of claim 1 wherein using said material,
Recognizing information associated with the spectral distribution shape of fluorescence obtained by irradiating the lithium secondary battery or capacitor with electromagnetic waves in a specific wavelength region, and identifying the lithium secondary battery or capacitor Method.