JP2012204182A - Heat-resistant flexible battery and method for manufacturing heat-resistant flexible battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a battery having both favorable heat resistance and flexibility.SOLUTION: A heat-resistant flexible battery 100 according to the present invention includes: a first heat-resistant flexible collector 210; a heat-resistant flexible positive electrode 220; a heat-resistant flexible separator 300; a second heat-resistant flexible collector 410; a heat-resistant flexible negative electrode 420; and an electrolyte-containing medium. The heat-resistant flexible positive electrode 220 is formed on the first heat-resistant flexible collector 210. The heat-resistant flexible negative electrode 420 is formed on the second heat-resistant flexible collector 410. The electrolyte-containing medium is filled between the heat-resistant flexible positive electrode 220 and the heat-resistant flexible negative electrode 420.

Description

  The present invention relates to a heat-resistant flexible battery and a method for producing a heat-resistant flexible battery.

  In the past, “a lithium secondary battery including a flexible separator” has been proposed (for example, see Patent Document 1). Since the separator has flexibility, this lithium secondary battery has flexibility.

JP 2005-63958 A

  However, recent lithium secondary batteries are required to have heat resistance as well as flexibility. In addition, the conventional lithium secondary battery includes many materials that cannot withstand 200 ° C., and the drying temperature for removing moisture cannot be increased to 200 ° C. Therefore, a highly heat resistant material and battery structure are required.

  The subject of this invention is providing the battery which has favorable heat resistance and flexibility.

(1)
A heat-resistant flexible battery according to the present invention includes a first heat-resistant flexible current collector, a heat-resistant flexible positive electrode, a heat-resistant flexible separator, a second heat-resistant flexible current collector, and a heat-resistant flexible battery. A negative electrode and an electrolyte-containing medium. The heat resistant flexible positive electrode is formed on the first heat resistant flexible current collector. The heat resistant flexible negative electrode is formed on the second heat resistant flexible current collector. The heat-resistant flexible negative electrode is disposed so as to face the heat-resistant flexible positive electrode with the heat-resistant flexible separator interposed therebetween. The electrolyte-containing medium is filled between the heat-resistant flexible positive electrode and the heat-resistant flexible negative electrode. In the present invention, “having heat resistance” means that it is composed of a structure and material that can withstand heat treatment up to 200 ° C. in the drying step prior to the step of injecting the electrolyte-containing medium. By performing a heat treatment at 200 ° C. in this drying step, water is completely removed from the inside of the battery, and deterioration of the battery due to moisture mixing is prevented. Furthermore, the heat-resistant flexible battery can be provided with heat resistance even when the battery is used by using the heat-resistant electrolyte-containing medium in a step after the step of injecting the electrolyte-containing medium. Hitherto, materials with high heat resistance such as active materials, separators, and binders have been proposed as heat-resistant materials for lithium secondary batteries. It was not enough. In the present invention, in addition to using an active material having heat resistance, a separator, and a binder, the insulating film and resin having heat resistance and the conductive film and resin can be properly used depending on the application. A battery having both good heat resistance and flexibility is provided.

  As a result of intensive studies by the inventor of the present application, it has been found that this heat-resistant flexible battery has both good heat resistance and flexibility.

(2)
It is preferable to further include the first electrical insulating resin, the second electrical insulating resin, and the third electrical insulating resin described in (1) above. The first electrically insulating resin is formed between the first heat-resistant flexible current collector and the heat-resistant flexible separator. The second electrically insulating resin is formed between the second heat-resistant flexible current collector and the heat-resistant flexible separator. The third electrically insulating resin is formed on the outer peripheral portion of the heat resistant flexible separator. The first electric insulating resin, the second electric insulating resin, and the third electric insulating resin are integrated and have a frame shape.

  A heat-resistant flexible battery surrounded by a first heat-resistant flexible current collector, a second heat-resistant flexible current collector, a first electrically insulating resin, a second electrically insulating resin, and a third electrically insulating resin The inside is sealed. Therefore, the heat-resistant flexible battery is easy to handle because there is no need to worry about liquid leakage of the filled electrolyte-containing medium. Therefore, a plurality of heat-resistant flexible batteries can be easily stacked in order to increase the voltage.

(3)
It is preferable to further include the frame-shaped heat-resistant adhesive film of (1) above. The heat resistant adhesive film surrounds the outer periphery of the heat resistant flexible separator, the heat resistant flexible positive electrode, and the heat resistant flexible negative electrode. The heat resistant adhesive film is formed between the first heat resistant flexible current collector and the second heat resistant flexible current collector.

  The inside of the heat-resistant flexible battery surrounded by the first heat-resistant flexible current collector, the second heat-resistant flexible current collector, and the heat-resistant adhesive film is sealed. Therefore, the heat-resistant flexible battery is easy to handle because there is no need to worry about liquid leakage of the filled electrolyte-containing medium. Therefore, a plurality of heat-resistant flexible batteries can be easily stacked in order to increase the voltage.

(4)
The heat-resistant flexible battery according to any one of the above (1) to (3) preferably has an active material layer. The active material layer is mainly composed of active material particles and porous polyimide resin. The porous polyimide resin binds the active material particles to each other.

  As a result of intensive studies by the inventor of the present application, it has been clarified that this heat-resistant flexible battery improves the charge / discharge cycle and increases the discharge capacity as compared with the conventional heat-resistant flexible battery by the active material layer. .

(5)
The heat-resistant flexible battery according to any one of the above (1) to (4) preferably further includes a first undercoat layer and a second undercoat layer. The first undercoat layer is formed on the first heat resistant flexible current collector. The second undercoat layer is formed on the second heat-resistant flexible current collector. The heat-resistant flexible positive electrode is formed on the first undercoat layer. The heat-resistant flexible negative electrode is formed on the second undercoat layer. When the undercoat layer is formed on the current collector, the “mixed polyimide resin solution with conductive filler” for forming the undercoat layer is heated for several tens of minutes at a temperature between 50 ° C. and 100 ° C. It is preferable to apply a slurry. By doing so, the mixture slurry is applied in a state where the undercoat layer is not completely solidified, so that the undercoat layer and the active material layer are well bonded.

  The first undercoat layer improves the adhesion between the first heat-resistant flexible current collector and the heat-resistant flexible positive electrode. The first undercoat layer may improve adhesion between the first heat-resistant flexible current collector, the heat-resistant flexible positive electrode, and the first electrically insulating resin or the heat-resistant adhesive film.

  Similarly, the second undercoat layer improves the adhesion between the second heat-resistant flexible current collector and the heat-resistant flexible negative electrode. The second undercoat layer also improves the adhesion between the second heat-resistant flexible current collector, the heat-resistant flexible negative electrode, and the second electrically insulating resin or heat-resistant adhesive film.

(6)
In the heat-resistant flexible battery laminate according to the present invention, the heat-resistant flexible battery according to any one of the above (1) to (5) includes the first heat-resistant flexible current collector and the second heat-resistant flexible current collector. A plurality of layers are stacked such that the body and the body overlap alternately.

  In the heat-resistant flexible battery laminate, a desired voltage can be easily obtained by appropriately adjusting the number of heat-resistant flexible batteries stacked.

(7)
It is preferable that the heat-resistant flexible battery of the above (1) further includes a heat-resistant flexible rib portion. The heat-resistant flexible rib portions are provided on the periphery of the heat-resistant flexible separator on both sides of the heat-resistant flexible separator. The heat-resistant flexible positive electrode and the heat-resistant flexible negative electrode are inserted into the internal space of the heat-resistant flexible rib portion. The electrolyte-containing medium is filled inside the heat-resistant flexible separator.

  When assembling the heat-resistant flexible battery, the heat-resistant flexible rib portion serves to assist the positioning of the installation positions of the heat-resistant flexible positive electrode and the heat-resistant flexible negative electrode. Therefore, the user can easily assemble the heat-resistant flexible battery.

(8)
The heat-resistant flexible battery of the above (7) has an active material layer. The active material layer is mainly composed of active material particles and porous polyimide resin. The porous polyimide resin has a porous structure, functions as a template material including the active material particles, binds the active material particles in the pores, and binds the current collector and the active material particles. It plays a role.

  As a result of intensive studies by the inventor of the present application, it has been clarified that this heat-resistant flexible battery improves the charge / discharge cycle and increases the discharge capacity as compared with the conventional heat-resistant flexible battery by the active material layer. .

(9)
It is preferable that the heat-resistant flexible battery of the above (7) or (8) further includes a first undercoat layer and a second undercoat layer. The first undercoat layer is formed on the first heat resistant flexible current collector. The second undercoat layer is formed on the second heat-resistant flexible current collector. The heat-resistant flexible positive electrode is formed on the first undercoat layer. The heat-resistant flexible negative electrode is formed on the second undercoat layer.

  The first undercoat layer improves the adhesion between the first heat-resistant flexible current collector, the heat-resistant flexible positive electrode, and the heat-resistant flexible rib portion. Similarly, the second undercoat layer improves the adhesion between the second heat-resistant flexible current collector, the heat-resistant flexible negative electrode, and the heat-resistant flexible rib portion.

(10)
The manufacturing method of the heat-resistant flexible battery according to the present invention includes a pasting step and a curing step. In the attaching step, the first heat-resistant flexible current collector on which the heat-resistant flexible positive electrode is formed and the second heat-resistant flexible current collector on which the heat-resistant flexible negative electrode is formed are electrically insulating resin precursors. Affixed to a heat-resistant flexible separator via a body paste. In the curing step, the electrically insulating resin precursor paste is cured.

  In this method of manufacturing a heat-resistant flexible battery, the adhesiveness between the heat-resistant flexible separator, the first heat-resistant flexible current collector, and the second heat-resistant flexible current collector is improved by the electrically insulating resin precursor paste. improves.

(11)
It is preferable that the manufacturing method of the heat-resistant flexible battery described in (10) further includes a coating step. In the application step, the electrically insulating resin precursor paste is applied while impregnating the outer peripheral portion of the heat-resistant flexible separator.

  In this method of manufacturing a heat-resistant flexible battery, the first heat-resistant flexible current collector, the second heat-resistant flexible battery, and the second heat-resistant flexible battery are applied by impregnating the outer peripheral portion of the heat-resistant flexible separator while being impregnated with the electrically insulating resin precursor paste. The inside of the heat-resistant flexible battery surrounded by the heat-resistant flexible current collector, the first electrically insulating resin, the second electrically insulating resin, and the third electrically insulating resin can be easily sealed.

(12)
It is preferable that the manufacturing method of the heat-resistant flexible battery of the above (10) or (11) further includes a lead electrode attaching step. In the extraction electrode attachment step, the extraction electrode is attached to at least one of the first heat-resistant flexible current collector and the second heat-resistant flexible current collector with a conductive resin precursor paste. In the curing step, the electrically insulating resin precursor paste and the conductive resin precursor paste are cured.

  In this method for manufacturing a heat-resistant flexible battery, the conductive resin precursor paste is applied to the heat-resistant flexible current collector and heated, whereby the extraction electrode is bonded to the heat-resistant flexible current collector. Therefore, in this heat-resistant flexible battery manufacturing method, metal impurities are less likely to be mixed as compared with the case where the extraction electrode and the heat-resistant flexible current collector are attached by spot welding. In addition, in this method for manufacturing a heat-resistant flexible battery, complicated operations are reduced as compared with the case where the extraction electrode and the heat-resistant flexible current collector are attached by ultrasonic welding. Furthermore, this heat-resistant flexible battery manufacturing method eliminates the need for expensive equipment for ultrasonic welding, thereby reducing the manufacturing cost of the heat-resistant flexible battery.

  The heat-resistant flexible battery according to the present invention has both good heat resistance and flexibility.

It is sectional drawing of the heat-resistant flexible battery concerning 1st Embodiment of this invention. It is sectional drawing of the heat-resistant flexible battery concerning the modification (A) of 1st Embodiment of this invention. It is sectional drawing of the heat-resistant flexible battery concerning the modification (B) of 1st Embodiment of this invention. It is an exploded view of the heat-resistant flexible battery concerning the modification (B) of 1st Embodiment of this invention. It is sectional drawing of the heat-resistant flexible battery concerning 2nd Embodiment of this invention. It is an exploded view of the heat-resistant flexible battery concerning 2nd Embodiment of this invention. It is sectional drawing of the heat-resistant flexible battery concerning the modification (A) of 2nd Embodiment of this invention. It is sectional drawing of the heat-resistant flexible battery laminated body concerning the modification (B) of 2nd Embodiment of this invention. It is sectional drawing of the heat-resistant flexible battery concerning 3rd Embodiment of this invention. It is an exploded view of the heat-resistant flexible battery concerning 3rd Embodiment of this invention. It is sectional drawing of the heat-resistant flexible battery concerning the modification (A) of 3rd Embodiment of this invention. It is sectional drawing of the heat-resistant flexible battery laminated body concerning the modification (B) of 3rd Embodiment of this invention.

-First embodiment-
As shown in FIG. 1, the heat-resistant flexible battery 100 according to the first embodiment of the present invention includes a first heat-resistant flexible current collector 210, a heat-resistant flexible positive electrode 220, and a first extraction electrode 230. A first conductive resin 240, a heat resistant flexible separator 300, a second heat resistant flexible current collector 410, a heat resistant flexible negative electrode 420, a second extraction electrode 430, and a second conductive resin. 440 and an electrolyte-containing medium and a packaging material (not shown). The heat-resistant flexible battery 100 is preferably a secondary battery, and more preferably a non-aqueous electrolyte secondary battery. In the present invention, “having heat resistance” means that it is composed of a structure and material that can withstand heat treatment up to 200 ° C. in the drying step prior to the step of injecting the electrolyte-containing medium.

  As the first heat-resistant flexible current collector 210, for example, a polyimide resin containing a conductive filler is used. The polyimide resin is obtained from, for example, a monomer type polyimide precursor or a polyamic acid type polyimide precursor. The monomer-type polyimide precursor is mainly composed of a tetracarboxylic acid diester compound and a diamine compound. For example, the monomer-type polyimide precursor is imidized by heating to have a high molecular weight to be a polyimide resin. The polyamic acid type polyimide precursor is mainly composed of a polyamic acid, and is imidized by heating to become a polyimide resin. The first heat-resistant flexible current collector 210 may be a single metal such as aluminum or stainless steel and alloys thereof, and graphite having conductivity, in addition to the conductive polyimide.

  The conductive filler functions as a conductive additive. Examples of the conductive filler include carbon black (oil furnace black, channel black, lamp black, thermal black, ketjen black, acetylene black), carbon nanotube, carbon nanofiber, fullerene, carbon microcoil, graphite (natural graphite, Artificial graphite) carbon black, carbon fiber short fibers (PAN-based carbon short fibers, pitch-based carbon short fibers) and the like are used. These conductive fillers may be used alone or in combination.

  The surface of the first heat-resistant flexible current collector 210 is preferably roughened in order to improve adhesion with the heat-resistant flexible positive electrode 220. The roughening of the first heat-resistant flexible current collector 210 is performed, for example, by subjecting the surface of the first heat-resistant flexible current collector 210 to a roughening process. Examples of the roughening treatment include a vapor deposition method, an etching method, and a polishing method. Examples of the vapor phase growth method include a sputtering method, a CVD method, and a vapor deposition method. Examples of the etching method include a physical etching method and a chemical etching method. Examples of the polishing method include polishing by sandpaper or polishing by a blast method.

  The heat-resistant flexible positive electrode 220 is formed on the first heat-resistant flexible current collector 210. The heat-resistant flexible positive electrode 220 has a positive electrode active material layer (not shown). The positive electrode active material layer is mainly composed of, for example, positive electrode active material particles and a positive electrode porous polyimide resin.

As the active material particles for the positive electrode, for lithium batteries, for example, lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium metal phosphate LiMPO ₄ (M = Fe, Mn, Co, Ni), lithium metal borate LiMBO ₃ (M = Fe, Mn, Co, Ni), lithium metal silicate Li ₂ MSiO ₄ (M = Fe, Mn, Co, Ni), lithium metal sulfate Lithium-containing transition metal oxides such as LiMSO ₄ (M = Fe, Mn, Co, Ni), FeF ₃ , TiS ₂ , FeS ₂ , sulfide-based polymer active materials are used as one type or a mixture of two or more types I can do it. Among these, from the viewpoint of heat resistance, lithium metal phosphate LiMPO ₄ (M = Fe, Mn, Co, Ni), lithium metal borate LiMBO ₃ (M = Fe, Mn, Co, Ni), lithium metal silicate Li ₂ MSiO ₄ (M = Fe, Mn, Co, Ni), lithium-containing transition metal oxides such as lithium metal sulfate LiMSO ₄ (M = Fe, Mn, Co, Ni), and sulfide-based polymer active materials having high heat resistance Is also preferably used. For sodium batteries, Fe ₂ (MnO ₄ ) ₃ , Fe ₂ (WO ₄ ) ₃ , Fe ₂ (SO ₄ ) ₃ , Li ₃ Fe ₂ (PO ₄ ) ₃ , FeF ₃ , NaFeO ₂ , TiS ₂ , Sodium metal battery positive electrode materials such as FeS ₂ and sulfide-based polymers can be used as one type or as a mixture of two or more types.

  The porous polyimide resin for the positive electrode has a porous structure in the positive electrode active material layer, functions as a template material including the active material particles for the positive electrode, binds the active material particles in the pores, It plays the role of binding the first heat-resistant flexible current collector 210 and the active material particles for the positive electrode. The porous polyimide resin for the positive electrode is obtained from, for example, a monomer type polyimide precursor. Further, the porous polyimide resin for the positive electrode may be the same as or different from the polyimide resin of the first heat-resistant flexible current collector 210 as long as it is porous.

  The porous polyimide resin for the positive electrode preferably contains a conductive filler that can be used as the material of the first heat-resistant flexible current collector 210. The conductive filler contained in the porous polyimide resin for the positive electrode may be the same as or different from the conductive filler of the first heat-resistant flexible current collector 210 described above.

  The first lead electrode 230 is electrically connected to the first heat-resistant flexible current collector 210 by a first conductive resin 240 having conductivity. As the first extraction electrode 230, for example, a conductive tape made of copper or the like is used. The first lead electrode 230 is preferably attached on the surface of the first heat-resistant flexible current collector 210. The first lead electrode 230 attached on the surface of the first heat-resistant flexible current collector 210 has a first lead electrode 230 as compared with the first lead electrode 230 attached to the periphery of the first heat-resistant flexible current collector 210. The contact area with the heat-resistant flexible current collector 210 can be increased. Therefore, the first lead electrode 230 can easily take out electricity from the first heat-resistant flexible current collector 210. The first extraction electrode 230 is made of, for example, aluminum, stainless steel and an alloy thereof, and conductive graphite.

  The first conductive resin 240 is formed from, for example, a conductive resin precursor paste. The conductive resin precursor paste includes, for example, a monomer type polyimide precursor or a polyamic acid type polyimide precursor, and a conductive filler. As the conductive filler, a conductive filler that can be used as the material of the first heat-resistant flexible current collector 210 can be used. A method of attaching the first extraction electrode 230 to the first heat-resistant flexible current collector 210 will be described later.

  As the heat-resistant flexible separator 300, a known separator for a lithium secondary battery having heat-resistant flexibility is used. For example, a polyimide resin separator, a glass nonwoven fabric separator, a pulp separator, an aramid separator, or a polyamideimide resin A separator made of metal is used.

  For the second heat-resistant flexible current collector 410, a polyimide resin containing a conductive filler is used. As the conductive filler and the polyimide resin, a conductive filler and a polyimide resin that can be used as the material of the first heat-resistant flexible current collector 210 are used. The second heat-resistant flexible current collector 410 is composed of simple metals such as copper, nickel, stainless steel, iron and tin, and alloys thereof, as well as conductive graphite, in addition to conductive polyimide. May be. Further, the surface of the second heat-resistant flexible current collector 410 is roughened in the same manner as the first heat-resistant flexible current collector 210 in order to improve the adhesion to the heat-resistant flexible negative electrode 420. It is preferable to face.

  The heat resistant flexible negative electrode 420 is formed on the second heat resistant flexible current collector 410. The heat-resistant flexible negative electrode 420 preferably has a layer structure having a negative electrode active material layer (not shown). Further, the heat-resistant flexible negative electrode 420 is disposed so as to face the heat-resistant flexible positive electrode 220 with the heat-resistant flexible separator 300 interposed therebetween. The negative electrode active material layer is mainly composed of negative electrode active material particles and negative electrode porous polyimide resin.

As the active material particles for the negative electrode, for lithium batteries, for example, graphite (C), lithium titanate (Li ₄ Ti ₅ O ₁₂ ), silicon (Si) particles, silicon oxide (SiO) particles, silicon alloy particles, A lithium battery negative electrode material such as tin (Sn) particles is used. Examples of silicon alloys include solid solutions of silicon and one or more other elements, intermetallic compounds of silicon and one or more other elements, and eutectic alloys of silicon and one or more other elements. . The active material particles for the negative electrode may include particles made of a material that is alloyed with lithium. Examples of such materials include germanium, tin, lead, zinc, magnesium, sodium, aluminum, gallium, indium, and alloys thereof. Further, in the case of a sodium battery, one kind or a mixture of two or more kinds of sodium metal battery anode materials such as hard carbon, tin (Sn), tin oxide (SnO), and tin alloy are used as the active material particles for the anode. Can be used.

  As a method for producing the silicon alloy, for example, an arc melting method, a liquid quenching method, a mechanical alloying method, a sputtering method, a chemical vapor deposition method, a firing method, or the like is used. In particular, as the liquid quenching method, various atomizing methods such as a single roll quenching method, a twin roll quenching method, a gas atomizing method, a water atomizing method, and a disk atomizing method are used.

  The active material particles for the negative electrode are core-shell type active material particles in which the above-described silicon (Si) particles, silicon oxide (SiO) particles, silicon alloy particles, tin (Sn) particles, and the like are coated with a metal or the like. May be. The core-shell type active material particles are produced by an electroless plating method, an electrolytic plating method, a chemical reduction method, a vapor deposition method, a sputtering method, a chemical vapor deposition method, or the like. The shell portion is preferably formed of the same metal as that of the second heat-resistant flexible current collector 410. The core-shell type active material particles greatly improve the bondability with the second heat-resistant flexible current collector 410. Therefore, the heat-resistant flexible battery 100 can obtain excellent charge / discharge cycle characteristics.

  The active material particles for the negative electrode may be surface-treated with a silane coupling agent. By treating the negative electrode active material particles in this manner, the negative electrode active material particles can be well dispersed in the negative electrode porous polyimide resin precursor, and the negative electrode porous polyimide. The binding property of the active material particles for the negative electrode to the resin can be enhanced.

  The porous polyimide resin for the negative electrode has a porous structure in the negative electrode active material layer, functions as a template material including the active material particles for the negative electrode, and binds the active material particles in the pores, It plays the role of binding the second heat-resistant flexible current collector 410 and the active material particles for the negative electrode. The porous polyimide resin is obtained from, for example, a monomer type polyimide precursor. The porous polyimide resin for the negative electrode may be the same as or different from the polyimide resin of the second heat-resistant flexible current collector 410 as long as it is porous.

  The porous polyimide resin for the negative electrode preferably contains a conductive filler that can be used as the material of the first heat-resistant flexible current collector 210. The conductive filler contained in the porous polyimide resin for the negative electrode may be the same as or different from the conductive filler of the second heat-resistant flexible current collector 410.

  The second extraction electrode 430 is electrically connected to the second heat-resistant flexible current collector 410 by a second conductive resin 440 having conductivity. As the second extraction electrode 430, for example, a conductive tape made of copper or the like is used. The second lead electrode 430 is preferably attached on the surface of the second heat-resistant flexible current collector 410. The second lead electrode 430 attached on the surface of the second heat-resistant flexible current collector 410 is second in comparison with the second lead electrode 430 attached on the periphery of the second heat-resistant flexible current collector 410. The contact area with the heat-resistant flexible current collector 410 can be increased. Therefore, the second extraction electrode 430 can easily extract electricity from the second heat-resistant flexible current collector 410.

  The second conductive resin 440 is formed from, for example, a conductive resin precursor paste. The conductive resin precursor paste includes, for example, a monomer type polyimide precursor or a polyamic acid type polyimide precursor, and a conductive filler. As the conductive filler, a conductive filler that can be used as the material of the first heat-resistant flexible current collector 210 can be used. A method for attaching the second extraction electrode 430 to the second heat-resistant flexible current collector 410 will be described later.

The electrolyte-containing medium is filled between the heat-resistant flexible positive electrode 220 and the heat-resistant flexible negative electrode 420. As the electrolyte-containing medium, a known electrolyte-containing medium for a lithium secondary battery is used. For example, a medium in which a lithium salt as an electrolyte is dissolved in an organic solvent can be used. As the organic solvent, it is preferable to use at least one selected from non-aqueous solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dimethyl ether, isopropyl methyl carbonate, vinylene carbonate, γ-butyrolactone, and acetonitrile. . As the electrolyte, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiI, LiClO ₄ or the like can be used when lithium is used as the negative electrode active material. From the viewpoint of heat resistance, a liquid electrolyte solution using an ionic liquid as a solvent is preferably used. Moreover, as an electrolyte used in the case of a sodium ion secondary battery, what dissolved the sodium salt which is electrolyte in the organic solvent can be used. As the organic solvent, it is preferable to use at least one selected from non-aqueous solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinylene carbonate, dimethyl ether, γ-butyrolactone, and acetonitrile. . As the electrolyte, one or more selected from NaPF ₆ , NaBF ₄ , NaClO ₄ , NaAsF ₆ , NaSbF ₆ , NaCF ₃ SO ₃ , NaN (SO ₂ CF ₃ ) ₂ , lower fatty acid sodium salt, NaAlCl _4, etc. are used. be able to. The concentration of the electrolyte may be 0.5 mol / l or more and 1.7 mol / l or less. The electrolyte-containing medium is not limited to liquid. For example, when the lithium ion secondary battery is a lithium polymer secondary battery, the electrolyte can be in a solid state (for example, a polymer gel).

  The packaging material accommodates the above-described configuration inside except for a part of the first extraction electrode 230 and a part of the second extraction electrode 430. As this packaging material, for example, a polyimide resin film, an aromatic polyamide resin film, a polyamideimide resin film, a polyalkylene terephthalate resin film, an aluminum laminate film, or the like is used.

<Effect in this embodiment>
This heat-resistant flexible battery 100 has both good heat resistance and flexibility.

<Modification>
(A)
As shown in FIG. 2, in the heat-resistant flexible battery 100a, the first undercoat layer 250 and the second undercoat layer 450 may be formed.

  The first undercoat layer 250 is formed between the first heat-resistant flexible current collector 210 and the heat-resistant flexible positive electrode 220. The first undercoat layer 250 improves the adhesion between the first heat-resistant flexible current collector 210 and the heat-resistant flexible positive electrode 220. The first undercoat layer 250 is formed of a resin that can be satisfactorily bonded to the porous polyimide resin for the positive electrode, and a conductive filler that imparts conductivity to the first undercoat layer 250.

  The second undercoat layer 450 is formed between the second heat-resistant flexible current collector 410 and the heat-resistant flexible negative electrode 420. The second undercoat layer 450 improves the adhesion between the second heat-resistant flexible current collector 410 and the heat-resistant flexible negative electrode 420. The second undercoat layer 450 is formed of a resin that can be satisfactorily adhered to the porous polyimide resin for the negative electrode, and a conductive filler that imparts conductivity to the second undercoat layer 450.

  The resin of the undercoat layers 250 and 450 is obtained from, for example, a monomer type polyimide precursor or a polyamic acid type polyimide precursor. As the conductive filler of the undercoat layers 250 and 450, a conductive filler that can be used as the material of the first heat-resistant flexible current collector 210 can be used.

  The first undercoat layer 250 improves the adhesion between the first heat-resistant flexible current collector 210 and the heat-resistant flexible positive electrode 220. Similarly, the second undercoat layer 450 improves the adhesion between the second heat-resistant flexible current collector 410 and the heat-resistant flexible negative electrode 420.

(B)
As shown in FIG. 3, the heat-resistant flexible battery 100 b may further include a first heat-resistant flexible rib portion 260 and a second heat-resistant flexible rib portion 460. The heat-resistant flexible rib portions 260 and 460 are provided on the outer periphery of the heat-resistant flexible separator 300 on both sides of the heat-resistant flexible separator 300, respectively.

  The heat-resistant and flexible rib portions 260 and 460 have a frame shape having an internal space, and can be obtained by punching a heat-resistant and flexible resin film into a square frame shape. As the heat-resistant flexible resin film, for example, a polyimide resin film, an aromatic polyamide resin film, a polyamideimide resin film, a polyalkylene terephthalate resin film, an aluminum laminate film, or the like is used. Moreover, it is preferable that the heat-resistant flexible ribs 260 and 460 are bonded to the heat-resistant flexible separator 300 via a heat-resistant adhesive (for example, SKYBOND series manufactured by IST Corporation). The heat resistant adhesive improves the adhesion between the heat resistant flexible rib portions 260 and 460 and the heat resistant flexible separator 300.

  The heat-resistant flexible positive electrode 220 is inserted into the internal space of the first heat-resistant flexible rib portion 260 (see particularly FIG. 4). Similarly, the heat-resistant flexible negative electrode 420 is inserted into the internal space of the second heat-resistant flexible rib portion 460. The electrolyte-containing medium is filled in the heat-resistant flexible separator 300.

  The first undercoat layer 250 improves the adhesion between the first heat-resistant flexible current collector 210, the heat-resistant flexible positive electrode 220, and the first heat-resistant flexible rib portion 260. Similarly, the second undercoat layer 450 improves adhesion between the second heat-resistant flexible current collector 410, the heat-resistant flexible negative electrode 420, and the second heat-resistant flexible rib portion 460. Note that the undercoat layers 250 and 460 may not be formed in order to reduce the manufacturing cost of the heat-resistant flexible battery 100b.

  When assembling the heat-resistant flexible battery 100b, the heat-resistant flexible rib portions 260 and 460 serve to assist the positioning of the heat-resistant flexible positive electrode 220 and the heat-resistant flexible negative electrode 420. Therefore, the user can easily assemble the heat-resistant flexible battery 100b.

-Second Embodiment-
As shown in FIGS. 5 and 6, the heat-resistant flexible battery 100 c according to the second embodiment of the present invention is different from the heat-resistant flexible battery 100 according to the first embodiment, and the first electrical insulating layer 510. The second electrical insulation layer 520 and the third electrical insulation layer 530 are further provided. In addition, about the structure which is common in the heat resistant flexible battery 100c which concerns on 2nd Embodiment, and the heat resistant flexible battery 100 which concerns on said 1st Embodiment, the description is abbreviate | omitted suitably.

  The first electrical insulating resin 510, the second electrical insulating resin 520, and the third electrical insulating resin 530 are integrated and have a frame shape (see particularly FIG. 6). Specifically, the first electrically insulating resin 510 is formed on the outer periphery of the heat resistant flexible separator 300 and between the first heat resistant flexible current collector 210 and the heat resistant flexible separator 300. The second electrically insulating resin 520 is formed on the outer periphery of the heat resistant flexible separator 300 and between the second heat resistant flexible current collector 410 and the heat resistant flexible separator 300. The third electrically insulating resin 530 is formed between the outer periphery of the heat resistant flexible separator 300 and between the first electrically insulating resin 510 and the second electrically insulating resin 520.

  The first electric insulating resin 510, the second electric insulating resin 520, and the third electric insulating resin 530 have heat-resistant flexibility, and the heat-resistant flexible separator 300 and the first heat-resistant flexible current collector. The adhesion between the body 210 and the second heat-resistant flexible current collector 410 is improved. The first electrically insulating resin 510, the second electrically insulating resin 520, and the third electrically insulating resin 530 are obtained from an electrically insulating resin precursor paste. The electrically insulating resin precursor paste is made of, for example, a monomer type polyimide precursor or a polyamic acid type polyimide precursor.

  The heat resistance surrounded by the first heat-resistant flexible current collector 210, the second heat-resistant flexible current collector 410, the first electrically insulating resin 510, the second electrically insulating resin 520, and the third electrically insulating resin 530. The inside of the flexible battery 100c is sealed in a state filled with an electrolyte-containing medium. In addition, it is preferable that the 1st electrical insulation resin 510 or the 2nd electrical insulation resin 520 is provided with the electrolyte solution injection port and the safety valve. The electrolyte solution injection port is for injecting the electrolyte-containing medium into the heat-resistant flexible battery 100c. After the electrolyte-containing medium is injected from the electrolyte solution injection port, the polyimide precursor is applied to the electrolyte solution injection port. The applied polyimide precursor is heat-treated at 100 ° C. to 200 ° C. and cured, whereby the electrolyte solution inlet is sealed, thereby preventing liquid leakage. The safety valve is for venting the gas inside the heat-resistant flexible battery 100c when the pressure inside the heat-resistant flexible battery 100c reaches a predetermined pressure.

<Method for producing heat-resistant flexible battery>
The manufacturing method of the heat-resistant flexible battery 100c includes an application step, a pasting step, a lead electrode attaching step, and a curing step.

  In the application step, the outer peripheral portion of the heat-resistant flexible separator 300 is applied while being impregnated with the electrically insulating resin precursor paste. In the case where the inside of the heat-resistant flexible battery 100c does not need to be sealed, the heat-resistant flexible separator 300 may not be impregnated with the electrically insulating resin precursor paste.

  In the attaching step, the first heat-resistant flexible current collector 210 formed on the heat-resistant flexible positive electrode 220 is attached to the heat-resistant flexible separator 300 via an electrically insulating resin precursor paste. Further, the second heat-resistant flexible current collector 410 formed on the heat-resistant flexible negative electrode 420 is attached to the heat-resistant flexible separator 300 via an electrically insulating resin precursor paste. Specifically, the first heat-resistant flexible current collector 210 is disposed so that the heat-resistant flexible positive electrode 220 faces the heat-resistant flexible separator 300. The second heat-resistant flexible current collector 410 is disposed so that the heat-resistant flexible negative electrode 420 faces the heat-resistant flexible separator 300.

  In the electrode attaching step, the first extraction electrode 230 is attached to the first heat-resistant flexible current collector 210 and the second extraction electrode 430 is attached to the second heat-resistant flexible current collector 410 with a conductive resin precursor paste. It is attached. In addition, an electrode attachment process may be performed before an application | coating process and may be performed between an application | coating process and a sticking process.

  In the curing step, the electrically insulating resin precursor paste and the conductive resin precursor paste are cured. The cured electrically insulating resin precursor paste becomes the first electrically insulating resin 510, the second electrically insulating resin 520, and the third electrically insulating resin 530. Further, the cured conductive resin precursor paste becomes the first conductive resin 240 and the second conductive resin 440. When the first conductive resin 240 and the second conductive resin 440 are not provided in the heat-resistant flexible battery 100c, the electrode attachment process is omitted, and the electrically insulating resin precursor paste is cured in the curing process. The curing step may be performed at a temperature of 150 ° C. to 400 ° C., preferably 200 ° C. to 300 ° C.

<Effect in this embodiment>
The heat resistance surrounded by the first heat-resistant flexible current collector 210, the second heat-resistant flexible current collector 410, the first electrically insulating resin 510, the second electrically insulating resin 520, and the third electrically insulating resin 530. The inside of the flexible battery 100c is sealed. Therefore, the heat-resistant flexible battery 100c is easy to handle because there is no need to worry about leakage of the filled electrolyte-containing medium. Therefore, a plurality of heat-resistant flexible batteries 100c can be easily stacked in order to increase the voltage.

  In the manufacturing method of the heat-resistant flexible battery 100c, the heat-resistant flexible separator 300, the first heat-resistant flexible current collector 210, and the second heat-resistant flexible current collector 410 are formed using an electrically insulating resin precursor paste. Improves the adhesion.

  In the manufacturing method of the heat-resistant flexible battery 100c, the first heat-resistant flexible current collector 210 is applied to the outer peripheral portion of the heat-resistant flexible separator 300 while being impregnated with the electrically insulating resin precursor paste. The inside of the heat-resistant flexible battery 100c surrounded by the second heat-resistant flexible current collector 410, the first electrically insulating resin 510, the second electrically insulating resin 520, and the third electrically insulating resin 530 can be easily obtained. Can be sealed.

  In this method of manufacturing the heat-resistant flexible battery 100c, the conductive resin precursor paste is applied to the heat-resistant flexible current collectors 210 and 410 and heated so that the extraction electrodes 230 and 430 are heat-resistant and flexible. Bonded to the electric bodies 210 and 410. Therefore, in this heat-resistant flexible battery manufacturing method, metal impurities are less likely to be mixed as compared with the case where the extraction electrodes 230 and 430 and the heat-resistant flexible current collectors 210 and 410 are attached by spot welding. Further, in this heat-resistant flexible battery manufacturing method, complicated work is reduced as compared with the case where the extraction electrodes 230 and 430 and the heat-resistant flexible current collectors 210 and 410 are attached by ultrasonic welding. . Furthermore, in this method for manufacturing a heat-resistant flexible battery, expensive equipment for ultrasonic welding is not required, so that the manufacturing cost of the heat-resistant flexible battery 100c can be reduced.

<Modification>
(A)
As shown in FIG. 7, the heat-resistant flexible battery 100 d may further include a first undercoat layer 250 and a second undercoat layer 450. The first undercoat layer 250 is formed on the first heat resistant flexible current collector 210. The second undercoat layer 450 is formed on the second heat resistant flexible current collector 410. The heat-resistant flexible positive electrode 220 and the first conductive resin 510 are formed on the first undercoat layer 250. The heat-resistant flexible negative electrode 420 and the second conductive resin 520 are formed on the second undercoat layer 450.

  The first undercoat layer 250 improves adhesion between the first heat-resistant flexible current collector 210, the heat-resistant flexible positive electrode 220, and the first conductive resin 510. Similarly, the second undercoat layer 450 improves the adhesion between the second heat-resistant flexible current collector 410, the heat-resistant flexible negative electrode 420, and the second conductive resin 520.

(B)
As shown in FIG. 8, in the heat-resistant flexible battery stack 600, the first heat-resistant flexible current collector 210 and the second heat-resistant flexible current collector 410 are overlapped so that two The heat-resistant flexible battery 100c may be stacked. In the heat resistant flexible battery stack 600, the lead electrodes 230 and 430 between the first heat resistant flexible current collector 210 and the second heat resistant flexible current collector 410 are omitted. The heat-resistant flexible battery 100c includes three or more heat-resistant flexible batteries 100c such that the first heat-resistant flexible current collector 210 and the second heat-resistant flexible current collector 410 are alternately overlapped. May be laminated.

  Instead of the adjacent first heat-resistant flexible current collector 210 and second heat-resistant flexible current collector 410, one heat-resistant flexible current collector may be used. A heat-resistant flexible positive electrode 220 is formed on one surface of the heat-resistant flexible current collector, and a heat-resistant flexible negative electrode 420 is formed on the other surface. Therefore, the heat-resistant flexible battery stack 600 provided with this heat-resistant flexible current collector has a bipolar stacked structure.

  In the heat-resistant flexible battery stack 600, a desired voltage can be easily obtained by appropriately adjusting the number of layers of the heat-resistant flexible battery 100c.

-Third embodiment-
As shown in FIGS. 9 and 10, the heat-resistant flexible battery 100 e according to the third embodiment of the present invention is different from the heat-resistant flexible battery 100 according to the first embodiment, and is a frame-shaped heat-resistant adhesive film. 700 is further provided.

  The heat-resistant adhesive film 700 has a frame shape having an internal space, and can be obtained by punching a heat-resistant flexible resin film into a square frame shape. As the heat-resistant flexible resin film, for example, a polyimide resin film, an aromatic polyamide resin film, a polyamideimide resin film, a polyalkylene terephthalate resin film, an aluminum laminate film, or the like is used.

  The heat resistant adhesive film 700 is disposed so as to surround the outer periphery of the heat resistant flexible separator 300, the heat resistant flexible positive electrode 220, and the heat resistant flexible negative electrode 420. In addition, the heat resistant flexible separator 300, the first heat resistant flexible current collector 210, and the second heat resistant flexible current collector 410 are bonded to the heat resistant adhesive film 700. Therefore, the heat resistant adhesive film 700 is formed between the first heat resistant flexible current collector 210 and the second heat resistant flexible current collector 410. In order to improve the adhesiveness, the heat-resistant adhesive film 700 is provided with a heat-resistant flexible separator 300 and a first heat-resistant flexible collector through a heat-resistant adhesive (for example, SKYBOND series manufactured by IST Corporation). It is preferable to adhere to the electric body 210 and the second heat-resistant flexible current collector 410.

  The inside of the heat-resistant flexible battery 100e surrounded by the first heat-resistant flexible current collector 210, the second heat-resistant flexible current collector 410, and the heat-resistant adhesive film 700 is hermetically sealed with an electrolyte-containing medium. Has been. The heat resistant adhesive film 700 is preferably provided with an electrolyte injection port and a safety valve.

<Effect in this embodiment>
The inside of the heat resistant flexible battery 100e surrounded by the first heat resistant flexible current collector 210, the second heat resistant flexible current collector 410, and the heat resistant adhesive film 700 is sealed. Therefore, the heat-resistant flexible battery 100e is easy to handle because there is no need to worry about leakage of the filled electrolyte-containing medium. Therefore, a plurality of heat-resistant flexible batteries 100e can be easily stacked in order to increase the voltage.

<Modification>
(A)
As shown in FIG. 11, the heat-resistant flexible battery 100 f may further include a first undercoat layer 250 and a second undercoat layer 450. The first undercoat layer 250 is formed on the first heat resistant flexible current collector 210. The second undercoat layer 450 is formed on the second heat resistant flexible current collector 410. The heat-resistant flexible positive electrode 220 and the heat-resistant adhesive film 700 are formed on the first undercoat layer 250. The heat-resistant flexible negative electrode 420 and the heat-resistant adhesive film 700 are formed on the second undercoat layer 450.

  The first undercoat layer 250 improves the adhesion between the first heat-resistant flexible current collector 210, the heat-resistant flexible positive electrode 220, and the heat-resistant adhesive film 700. The second undercoat layer 450 improves the adhesion between the second heat-resistant flexible current collector 410, the heat-resistant flexible negative electrode 420, and the heat-resistant adhesive film 700.

(B)
As shown in FIG. 12, in the heat-resistant flexible battery stack 600e, the first heat-resistant flexible current collector 210 and the second heat-resistant flexible current collector 410 are alternately overlapped with each other. The heat-resistant flexible battery 100e may be stacked. In the heat-resistant flexible battery stack 600e, three or more heat-resistant flexible batteries 100e are alternately overlapped with the first heat-resistant flexible current collector 210 and the second heat-resistant flexible current collector 410. Thus, they may be laminated.

  Instead of the adjacent first heat-resistant flexible current collector 210 and second heat-resistant flexible current collector 410, one heat-resistant flexible current collector may be used. A heat-resistant flexible positive electrode 220 is formed on one surface of the heat-resistant flexible current collector, and a heat-resistant flexible negative electrode 420 is formed on the other surface. Therefore, the heat-resistant flexible battery stack 600e provided with this heat-resistant flexible current collector has a bipolar stacked structure.

  In the heat resistant flexible battery stack 600e, a desired voltage can be easily obtained by appropriately adjusting the number of layers of the heat resistant flexible battery 100e.

100, 100a, 100b, 100c, 100d, 100e, 100f Heat-resistant flexible battery 210 First heat-resistant flexible current collector 220 Heat-resistant flexible positive electrode 230 First extraction electrode (extraction electrode)
250 1st undercoat layer 260 1st heat-resistant flexible rib part (heat-resistant flexible rib part)
300 heat-resistant flexible separator 410 second heat-resistant flexible current collector 420 heat-resistant flexible negative electrode 430 second extraction electrode (extraction electrode)
450 1st undercoat layer 460 2nd heat resistant flexible rib part (heat resistant flexible rib part)
510 First Electrical Insulating Resin 520 Second Electrical Insulating Resin 530 Third Electrical Insulating Resin 600, 600e Heat Resistant Flexible Battery 700 Heat Resistant Adhesive Film

Claims (12)

A first heat-resistant flexible current collector;
A heat-resistant flexible positive electrode formed on the first heat-resistant flexible current collector;
A heat-resistant flexible separator;
A second heat resistant flexible current collector;
A heat-resistant flexible negative electrode formed on the second heat-resistant flexible current collector and disposed to face the heat-resistant flexible positive electrode across the heat-resistant flexible separator;
A heat-resistant flexible battery comprising an electrolyte-containing medium filled between the heat-resistant flexible positive electrode and the heat-resistant flexible negative electrode. A first electrically insulating resin formed between the first heat-resistant flexible current collector and the heat-resistant flexible separator;
A second electrically insulating resin formed between the second heat-resistant flexible current collector and the heat-resistant flexible separator;
A third electrically insulating resin formed on the outer periphery of the heat-resistant flexible separator,
2. The heat-resistant flexible battery according to claim 1, wherein the first electrically insulating resin, the second electrically insulating resin, and the third electrically insulating resin are integrated and have a frame shape. The heat-resistant flexible separator, the heat-resistant flexible positive electrode, and a frame-shaped heat-resistant adhesive film surrounding an outer periphery of the heat-resistant flexible negative electrode;
The heat resistant flexible battery according to claim 1, wherein the heat resistant adhesive film is formed between the first heat resistant flexible current collector and the second heat resistant flexible current collector.   2. At least one of the heat-resistant flexible positive electrode and the heat-resistant flexible negative electrode has an active material layer mainly composed of active material particles and a porous polyimide resin that binds the active material particles to each other. The heat-resistant flexible battery as described in any one of -3. A first undercoat layer formed on the first heat-resistant flexible current collector;
A second undercoat layer formed on the second heat-resistant flexible current collector,
The heat-resistant flexible positive electrode is formed on the first undercoat layer,
The heat-resistant flexible battery according to any one of claims 1 to 4, wherein the heat-resistant flexible negative electrode is formed on the second undercoat layer.   The heat-resistant flexible battery according to claim 1, wherein the first heat-resistant flexible current collector and the second heat-resistant flexible current collector are alternately overlapped. A heat-resistant flexible battery laminate to be laminated. A heat-resistant flexible rib portion provided on a peripheral portion of the heat-resistant flexible separator on both surfaces of the heat-resistant flexible separator;
The heat-resistant flexible positive electrode and the heat-resistant flexible negative electrode are inserted into an internal space of the heat-resistant flexible rib portion,
The heat resistant flexible battery laminate according to claim 1, wherein the electrolyte-containing medium is filled in the heat resistant flexible separator.   8. At least one of the heat-resistant flexible positive electrode and the heat-resistant flexible negative electrode has an active material layer mainly composed of active material particles and a porous polyimide resin that binds the active material particles. 2. A heat-resistant flexible battery laminate according to 1. A first undercoat layer formed on the first heat-resistant flexible current collector;
A second undercoat layer formed on the second heat-resistant flexible current collector,
The heat-resistant flexible positive electrode is formed on the first undercoat layer,
The heat-resistant flexible battery according to claim 7 or 8, wherein the heat-resistant flexible negative electrode is formed on the second undercoat layer. The first heat-resistant flexible current collector on which the heat-resistant flexible positive electrode is formed and the second heat-resistant flexible current collector on which the heat-resistant flexible negative electrode is formed are passed through an electrically insulating resin precursor paste. Affixing step to affix to the heat-resistant flexible separator,
A heat-resistant flexible battery manufacturing method comprising: a curing step of curing the electrical insulating resin precursor paste.   The method for manufacturing a heat-resistant flexible battery according to claim 10, further comprising an application step of applying the electrical insulating resin precursor paste while impregnating the outer peripheral portion of the heat-resistant flexible separator. A conductive resin precursor paste, further comprising a lead electrode attaching step of attaching a lead electrode to at least one of the first heat-resistant flexible current collector and the second heat-resistant flexible current collector;
The method for manufacturing a heat-resistant flexible battery according to claim 10 or 11, wherein, in the curing step, the electrically insulating resin precursor paste and the conductive resin precursor paste are cured.

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