WO2011055429A1 - 電池及び電池システム - Google Patents
電池及び電池システム Download PDFInfo
- Publication number
- WO2011055429A1 WO2011055429A1 PCT/JP2009/068831 JP2009068831W WO2011055429A1 WO 2011055429 A1 WO2011055429 A1 WO 2011055429A1 JP 2009068831 W JP2009068831 W JP 2009068831W WO 2011055429 A1 WO2011055429 A1 WO 2011055429A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- battery
- exterior body
- identification
- hydrogen sulfide
- positive electrode
- Prior art date
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/488—Cells or batteries combined with indicating means for external visualization of the condition, e.g. by change of colour or of light density
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/3644—Constructional arrangements
- G01R31/3646—Constructional arrangements for indicating electrical conditions or variables, e.g. visual or audible indicators
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
- H01M2008/147—Fuel cells with molten carbonates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a battery and a battery system including a sulfur-based material.
- Patent Documents 1 to 4 propose a battery using sulfide-based crystallized glass as a solid electrolyte.
- Sulfide-based solid electrolytes exhibit high ionic conductivity, and can increase the output of a solid battery.
- sulfide-based solid electrolytes have low water resistance, react with moisture to generate hydrogen sulfide, ionic conductivity is lowered, and the battery may be deteriorated.
- Patent Document 5 proposes an all-solid lithium secondary battery in which a hydrogen sulfide sensor is arranged in an outer package of a solid battery and hydrogen sulfide generated inside the battery can be detected by the sensor. .
- the present invention has been made in view of the above, and it is possible to identify the presence or absence of hydrogen sulfide generation inside a battery with a simple structure, and thereby to determine the presence or absence of battery deterioration and to provide a battery and battery system with excellent reliability. The issue is to provide.
- the present invention has the following configuration. That is, The first aspect of the present invention includes a power generation unit including a sulfur-based material and an identification unit that changes color by chemically reacting with hydrogen sulfide in the exterior body, and the identification unit is visible from the outside of the exterior body. It is a battery.
- the “exterior body” is not particularly limited in material and shape as long as it can enclose the power generation section. Etc. can be used. In addition, it is good also as a battery pack by preparing several exterior bodies which included the electric power generation part, and enclosing these further in an exterior body. “Exterior body” refers to the inner side of the outer surface (outer wall surface) of the outer body.
- the “sulfur-based material” is one in which sulfur or a sulfur compound is contained in at least a part of the compounds constituting the material.
- a solid electrolyte material of Li—AS (A is at least one selected from the group consisting of P, Ge, B, Si, and I) can be exemplified.
- the “power generation unit including a sulfur-based material” is a power generation unit including a sulfur-based material at least in part.
- the positive electrode layer, the solid electrolyte layer, or the negative electrode layer includes a sulfur-based material.
- the power generation unit can be mentioned.
- the exterior body may be provided with a viewing window.
- the “visual window” is not particularly limited as long as it is a window that allows the inside of the exterior body to be visually recognized from the outside of the exterior body. Thereby, the presence or absence of discoloration of the identification part provided in the exterior body can be easily confirmed, and the presence or absence of deterioration of the battery can be easily identified.
- the identification portion is preferably made of a material containing any one of Cu, Ni, Fe, Ag, Zn, Pb and Mn. This is because the color changes significantly by reacting with hydrogen sulfide, and the presence or absence of deterioration of the battery can be identified more easily.
- the exterior body includes a power generation unit including a sulfur-based material, and at least part of the identification means that changes color by chemically reacting with hydrogen sulfide is provided in a part of the exterior body. It is a battery.
- the identification means is provided in a part of the exterior body
- the identification means is attached to the exterior body so that the presence or absence of hydrogen sulfide generation in the battery can be identified. It is not particularly limited as long as it is provided, for example, a hole is provided in the exterior body, and the identification means is detachably inserted into the hole, or the identification means is detachably fitted, or the identification means by the exterior body It can be set as the form etc. which are pinched
- the identification means is made of a material containing any one of Cu, Ni, Fe, Ag, Zn, Pb and Mn. This is because the color changes significantly by reacting with hydrogen sulfide, and the presence or absence of deterioration of the battery can be identified more easily.
- a battery containing a sulfur-based material is provided in a fluid flow passage, and at least a part of the identification means that changes color by chemically reacting with hydrogen sulfide is located downstream of the battery in the fluid flow direction.
- a battery system is provided.
- the “fluid flow passage” means that when a fluid flow is generated in one direction (downstream direction) from the battery, or when generated, hydrogen sulfide generated from the battery is moved in the downstream direction.
- the passage is not particularly limited as long as it is a movable passage, and may be a duct, for example.
- the fluid flow includes that the gas generated from the battery naturally diffuses due to the concentration gradient. That is, the “fluid flow passage” is not limited to the one that intentionally generates a fluid flow by intake and exhaust using a blower or the like. However, in order to make the hydrogen sulfide generated from the battery reach the discriminating means more reliably, it is preferable to generate an intentional fluid flow in the fluid flow passage.
- the identification means is provided on the downstream side in the fluid flow direction with respect to the battery” means that the identification means is provided at a position where gas generated from the battery reaches or passes.
- the identification means is made of a material containing any one of Cu, Ni, Fe, Ag, Zn, Pb and Mn. This is because the color changes significantly by reacting with hydrogen sulfide, and the presence or absence of deterioration of the battery can be identified more easily.
- the identification portion that changes color by chemically reacting with hydrogen sulfide is provided inside the exterior body, and the identification portion is visible from the outside of the exterior body.
- the identification portion is visible from the outside of the exterior body.
- the exterior body since the identification means that is at least partially discolored by chemical reaction with hydrogen sulfide is provided in a part of the exterior body, the exterior body depends on whether the identification means is discolored or not. The presence or absence of hydrogen sulfide generation inside the battery can be confirmed, and the presence or absence of battery deterioration can be identified with a simple structure.
- the identification means for discoloring at least a part by chemical reaction with hydrogen sulfide is provided on the downstream side of the battery, depending on the presence or absence of the color change of the identification means, Whether or not hydrogen sulfide gas is generated can be confirmed, and the presence or absence of battery deterioration can be identified with a simple structure.
- FIG. 1 is a diagram schematically showing the appearance of a battery 10.
- FIG. FIG. 2 is a diagram schematically showing a cross section taken along the line II-II in FIG. 1.
- FIG. 3 is a diagram schematically showing a cross section taken along the line III-III in FIG. 1.
- FIG. 6 is a diagram for explaining a modified example of the battery 10. 1 is a diagram schematically showing the appearance of a battery 100.
- FIG. FIG. 6 is a diagram schematically showing a cross section taken along line VI-VI in FIG. 5. It is a figure for demonstrating the identification means 150.
- FIG. It is a figure which shows the structure of the insertion part 151 which concerns on the identification means 150.
- FIG. 2 is a diagram for explaining a battery system 200.
- FIG. 6 is a diagram for explaining a battery configuration according to Example 2.
- the present invention will be described by exemplifying an all-solid lithium secondary battery using a sulfide-based solid electrolyte.
- the present invention is not limited to such a form, and hydrogen sulfide can be generated in the battery.
- This battery for example, a molten carbonate fuel cell, a sodium sulfur battery, etc.
- a molten carbonate fuel cell for example, a molten carbonate fuel cell, a sodium sulfur battery, etc.
- FIGS. 1 to 3 are schematic views for explaining the external appearance and internal structure of a battery 10 according to a first embodiment of the present invention.
- 1 is an external view of the battery 10 as viewed from the side where the identification member 30 functioning as the identification unit is viewed
- FIG. 2 is a cross-sectional view taken along the line II-II in FIG. 1
- FIG. Fig. 3 schematically shows a cross section taken along line III-III.
- the battery 10 includes a positive electrode layer 21, a negative electrode layer 22, a solid electrolyte layer 23 provided between the positive electrode layer 21 and the negative electrode layer 22, and a positive electrode current collector 24 inside the outer package 15.
- the power generation unit 20 includes a negative electrode current collector 25, a positive electrode terminal 26 attached to the positive electrode current collector 24, and a negative electrode terminal 27 attached to the negative electrode current collector 25.
- the positive electrode terminal 26 and the negative electrode terminal 27 are provided so as to protrude from the inside of the exterior body 15 to the outside, and thereby electric energy can be taken out to the outside.
- the battery 10 has a hole 35 provided in a part of the outer package 15, a transparent member 31 provided on the inner side of the hole 35, and an inner side of the transparent member 31. Is provided with an identification member 30.
- a space 36 exists inside the exterior body 15, and the gas generated from the power generation unit 20 can reach the identification member 30 through the space 36.
- the exterior body 15 of the battery 10 is not particularly limited as long as it can appropriately accommodate the power generation unit 20 and the identification member 30 described later. 1 to 3, the power generation unit 20 and the like are laminated and inserted into the exterior body 15, that is, as the exterior body 15, a laminate film in which an aluminum foil and a resin film are laminated is used.
- the exterior body 15 is not limited to this form, and a housing made of aluminum or the like may be used.
- the shape of the exterior body 15 is not particularly limited as long as it can accommodate the power generation unit 20 and the like appropriately.
- a hole 35 is provided in the exterior body 15.
- the shape and size of the hole 35 are not particularly limited as long as the identification member 30 inside the exterior body 15 is visible. Further, as shown in FIG. 3, a predetermined space 36 is provided in the exterior body 15 so that the gas generated from the power generation unit 20 can reach the identification member 30.
- the space 36 may be a space generated by generating gas inside the battery 10. That is, it is not necessary to provide the space 36 in the exterior body 15 in advance, as long as the gas generated inside the battery 10 can reach the identification member 30.
- the power generation unit 20 is housed in the exterior body 15, and includes a positive electrode current collector 24 and a positive electrode layer 21 provided on at least one surface of the positive electrode current collector 24, a negative electrode current collector 25, and the negative electrode current collector. 25, a negative electrode layer 22 provided on at least one surface, and a solid electrolyte layer 23 provided between the positive electrode layer 21 and the negative electrode layer 22.
- the positive electrode layer 21 is a layer containing a positive electrode active material and a solid electrolyte, and may optionally contain a conductive additive, a binder, and the like.
- the active materials include LiCoO 2 , LiNiO 2 , Li 1 + x Ni 1/3 Mn 1/3 Co 1/3 O 2 , LiMn 2 O 4 , Li 1 + x Mn 2 Heterogeneous element-substituted Li—Mn spinel, Li x TiO y , LiMPO 4 (M is represented by —xy M y O 4 (M is one or more selected from Al, Mg, Co, Fe, Ni, Zn)) Fe, Mn, Co, or Ni), V 2 O 5 , MoO 3 , TiS 2 , graphite, carbon materials such as hard carbon, LiCoN, Li x Si y O z , lithium metal or lithium alloy (LiM, M is Sn, Si
- the positive and negative potentials are compared by comparing the charge and discharge potentials of two types of compounds, and the negative potential is negative.
- the solid electrolyte one containing at least lithium element and sulfur element is used.
- LiGe 0.25 P 0.75 S 4 , Li 2 S—B 2 S 3 , Li 2 S—SiS 2 , or those obtained by adding LiI, Li 2 PO 4, or the like can be used.
- the mixing ratio of the positive electrode active material and the solid electrolyte is not particularly limited as long as the mixing ratio is such that the battery 10 can operate.
- the conductive auxiliary agent conventional ones can be used without any particular limitation.
- a carbon material such as acetylene black is preferably used.
- a conventional binder can be used without any particular limitation.
- the positive electrode current collector 24 is not particularly limited as long as it is a current collector used for the battery 10 containing a sulfur-based material.
- a metal foil, a metal mesh, a metal vapor deposition film, or the like can be used.
- metal foils and meshes such as Al, V, Au, Pt, Mg, Ti, Co, and stainless steel, or films such as polyamide, polyimide, PET, PPS, and polypropylene, glass, silicon plates, etc.
- a material such as V, Al, Pt, Au, or the like deposited on the substrate can be used.
- the thickness and size of the positive electrode current collector 24 are not particularly limited.
- the positive electrode layer 21 can be formed on the positive electrode current collector 24 by preparing a positive electrode paste containing each of the above substances, and applying and drying the positive electrode current collector 24 on the positive electrode current collector 24.
- the means for applying the positive electrode paste is not particularly limited, and can be applied using a known means such as a doctor blade.
- the thickness of the positive electrode layer 21 after drying is not particularly limited. 2 illustrates an example in which the positive electrode layer 21 is provided only on one surface side of the positive electrode current collector 24, but the positive electrode layer 21 may be provided on both surfaces of the positive electrode current collector 24. Good.
- the negative electrode layer 22 is a layer containing a negative electrode active material and a solid electrolyte, and may optionally contain a conductive additive, a binder, and the like.
- the negative electrode active material used when the battery 10 is an all-solid lithium secondary battery is as described above. That is, among the above-described active materials, those showing a noble potential by comparing the charge / discharge potentials of two kinds of compounds can be used as the positive electrode active material, and those showing a base potential can be used as the negative electrode active material.
- the solid electrolyte as in the case of the positive electrode layer 21, one containing at least lithium element and sulfur element is used, and the above-described solid electrolyte can be used.
- the mixing ratio of the negative electrode active material and the solid electrolyte is not particularly limited as long as the mixing ratio is such that the battery 10 can operate.
- the conductive auxiliary agent and the binder conventional ones can be used without particular limitation, and those described above can be used.
- the negative electrode current collector 25 is not particularly limited as long as it is a current collector used for the battery 10 containing a sulfur-based material.
- a metal foil, a metal mesh, a metal vapor deposition film, or the like can be used.
- metal foils and meshes such as stainless steel, Al, V, Au, Pt, Mg, Ti, Co, or on films such as polyamide, polyimide, PET, PPS, polypropylene, glass, silicon plates, etc.
- a material such as V, Al, Pt, Au, or the like deposited on the substrate can be used.
- the thickness and size of the negative electrode current collector 25 are not particularly limited.
- the negative electrode layer 22 can be formed on the negative electrode current collector 25 by preparing a negative electrode paste containing each of the above substances and applying and drying the negative electrode current collector 25 on the negative electrode current collector 25.
- the means for applying the negative electrode paste is not particularly limited, and can be applied using a known means such as a doctor blade.
- the thickness of the negative electrode layer 22 after drying is not particularly limited. 2 illustrates an example in which the negative electrode layer 22 is provided only on one surface side of the negative electrode current collector 25, but the negative electrode layer 22 may be provided on both surfaces of the negative electrode current collector 25. Good.
- the solid electrolyte layer 23 is a layer provided between the positive electrode layer 21 and the negative electrode layer 22 and is not particularly limited as long as it is made of a sulfide-based solid electrolyte material.
- the sulfide-based solid electrolyte material the same solid electrolytes as those contained in the positive electrode layer 21 and the negative electrode layer 22 can be used.
- the formation method of the solid electrolyte layer 23 is not particularly limited as long as the solid electrolyte layer 23 can be provided between the positive electrode layer 21 and the negative electrode layer 22.
- a solid electrolyte a paste containing a solid electrolyte
- a solid electrolyte layer 23 can be formed on the positive electrode layer 21.
- the solid electrolyte layer 23 is appropriately provided between the positive electrode layer 21 and the negative electrode layer 22 by superimposing the negative electrode current collector 25 and the negative electrode layer 22 on the formed solid electrolyte layer 23. Can do.
- the positive electrode layer 21 and the positive electrode current collector 24 may be overlapped.
- the thickness of the solid electrolyte layer after drying is not particularly limited. In this way, the power generation unit 20 including the positive electrode current collector 24, the positive electrode layer 21, the solid electrolyte layer 23, the negative electrode layer 22, and the negative electrode current collector 25 in this order is manufactured.
- the positive electrode terminal 26 is attached to a part of the positive electrode current collector 24 (an uncoated portion of the positive electrode layer 21), and enables electric energy generated in the power generation unit 20 to be taken out to the outside.
- a known metal terminal can be used without any particular limitation.
- a tab made of stainless steel can be used as the positive electrode terminal 26.
- the shape and size of the positive electrode terminal 26 are not particularly limited as long as the shape and size are such that electric energy can be taken out from the inside of the battery 10 to the outside.
- the attachment of the positive electrode terminal 26 to the positive electrode current collector 24 is not particularly limited.
- the positive electrode terminal 26 can be attached to the positive electrode current collector 24 by welding using a known welding means. .
- the negative electrode terminal 27 is attached to a part of the negative electrode current collector 25 (an uncoated portion of the negative electrode layer 22), and enables electric energy generated in the power generation unit 20 to be taken out to the outside.
- a known metal terminal can be used without particular limitation.
- a tab made of stainless steel can be used as the negative electrode terminal 27.
- the shape and size of the negative electrode terminal 27 are not particularly limited as long as the shape and size are such that electric energy can be taken out from the inside of the battery 10 to the outside.
- the attachment of the negative electrode terminal 27 to the negative electrode current collector 25 is not particularly limited.
- the negative electrode terminal 27 can be attached to the negative electrode current collector 25 by welding using a known welding means. .
- FIG. 2 an example in which one power generation unit 20 and a pair of positive terminals 26 and 27 are provided in the exterior body 15 is illustrated, but the exterior body 15 includes a plurality of power generation units and terminals. It may be done. Moreover, it is good also as what laminated
- the identification member 30 is a member that functions as an identification unit for identifying the presence or absence of hydrogen sulfide generation inside the battery 10 (inside the outer package 15), and includes a material that changes color by chemically reacting with hydrogen sulfide. ing.
- the material is not particularly limited as long as it is discolored by chemically reacting with hydrogen sulfide, but it is discolored by reacting with metals other than titanium, tungsten, chromium and stainless steel, or with hydrogen sulfide. Organic compounds can be used.
- the identification member 30 as described above is installed in the exterior body 15 in the form of a film or a lump, and is visible from the outside of the exterior body 15 through a hole 35 provided in the exterior body 15 and a transparent member 31 described later.
- the presence or absence of hydrogen sulfide generation in the battery 10 can be identified by the degree of discoloration of the identification member 30.
- the transparent member 31 is a member provided inside the exterior body 15 so as to close the hole 35 provided in the exterior body 15, and functions as a viewing window that allows the inside of the battery 10 to be visually recognized.
- the transparent member 31 is not particularly limited as long as the transparent member 31 is transparent so that the inside of the exterior body 15 can be visually recognized from the outside, and a resin such as polyethylene resin, acrylic resin, polypropylene resin, glass, transparent ceramics, or the like. Can be used.
- the transparent member 31 is attached to the hole 35 portion of the exterior body 15 by a known welding method, adhesion method, fixing method, or the like.
- the transparent member 31 is preferably a resin film made of polymethyl methacrylate resin, polycarbonate, polyethylene, or the like because it can be easily heat-welded to the outer package 15.
- the identification member 30 is installed inside the exterior body 15 so as to be visible from the outside of the exterior body 15 through the hole 35 (and the transparent member 31).
- a material capable of forming the identification member 30 is vapor-deposited on a transparent member 31 made of a resin film using a known sputtering apparatus or the like, and then the vapor-deposited film is an exterior body.
- the transparent member 31 is thermally welded to the periphery of the hole 35 so that the identification member 30 can be appropriately installed inside the exterior body 15.
- the battery 10 includes the power generation unit 20 including a sulfur-based material and the identification member 30 that changes color by chemically reacting with hydrogen sulfide, and is provided in the exterior body 15. Since the identification member 30 is visible from the outside of the exterior body 15 through the formed hole 35, the presence or absence of internal hydrogen sulfide from the exterior of the exterior body 15 is determined depending on whether or not the identification member 30 is discolored. It can be confirmed, and the presence or absence of deterioration of the battery 10 can be identified with a simple structure. Moreover, since the transparent member 31 that functions as a visual recognition window is provided on the exterior body 15, the identification member 30 provided inside the exterior body 15 can be easily confirmed.
- FIG. 4 is a diagram for explaining a battery 10 ′ that is a modification of the battery 10 according to the first embodiment.
- the upper side of the paper is the outer side of the outer package 15 ′
- the lower side of the paper is the inner side of the outer package 15 ′.
- only the portion where the identification member 30 and the transparent member 31 are provided in the outer package 15 ′ is shown in an enlarged manner, and other battery configurations can be the same as those of the battery 10.
- a casing is used as the exterior body 15 ′ for the battery 10 ′.
- the exterior body 15 ′ can be a housing made of aluminum, for example.
- the thickness of the wall of the exterior body 15 ′ is not particularly limited as long as the identification member 30 and the transparent member 31 can be appropriately installed.
- Concave portions 16 and 16 are provided in a part of the exterior body 15 ′, and a hole 35 ′ is provided in a substantially central portion of the concave portions 16 and 16.
- the identification member 30 is deposited on the surface of the transparent member 31, and the outer edge of the transparent member 31 is a peripheral portion of the hole 35 ′ (recessed portion 16;
- the transparent member 31 is installed from the outside of the exterior body 15 ′ so as to be placed on a part of the exterior body 15 ′.
- the welding members 17 and 17 are fitted into the recesses 16 and 16 so as to press the outer edge of the placed transparent member 31, and the welding members 17 and 17 are welded to the exterior body 15 ′.
- the transparent member 31 is attached to the exterior body 15 ′, and the identification member 30 is provided on the inner side of the exterior body 15 ′.
- the welding members 17 and 17 are made of a material that can be welded to the exterior body 15 ′, for example, aluminum.
- a hole 18 is provided at substantially the center of the welding members 17, 17, and the identification means 30 can be visually recognized through the transparent member 31. Even in such a form, since the identification member 30 can be visually recognized from the outside of the exterior body 15 ′, hydrogen sulfide in the battery 10 ′ from the outside of the exterior body 15 ′ can be determined depending on whether the identification member 30 is discolored. The presence or absence of occurrence can be confirmed, and the presence or absence of deterioration of the battery 10 ′ can be identified with a simple structure.
- FIGS. 5 and 6 are schematic views for explaining the external appearance and internal structure of a battery 100 according to a second embodiment of the present invention.
- FIG. 5 is an external view of the battery 100 as viewed from the side where the identification unit 130 is provided
- FIG. 6 schematically shows a cross-section taken along the line VI-VI of FIG.
- the battery 100 includes an exterior body 115, and the interior of the exterior body 115 includes unit cells 120, 120,... Each having a power generation unit including a sulfur-based material. 120, 120,... Are provided.
- a hole 135 is provided in a part of the exterior body 115, and the identification unit 150 is removably inserted into the hole 135 from the outside of the exterior body 115.
- the identification unit 150 includes an insertion portion 151 and a support body 155, and the insertion portion 151 protrudes into the exterior body 115. Further, the support body 155 has a size and shape so as not to be inserted into the hole 135 from the inside, so that the identification means 150 can be easily pulled out.
- a space 130 is provided inside the exterior body 115, and gas generated from each single cell 120, 120,... Can reach the insertion portion 151 of the identification unit 150 through the space 130.
- the exterior body 115 is a housing made of aluminum. Further, a hole 135 is provided in a part of the exterior body 115. The hole 135 has such a size and shape that the insertion portion 151 of the identification means 150 can be inserted and the support 155 does not enter the inside.
- the unit cell 120 is a unit cell including a power generation unit including a sulfur-based material.
- the power generation unit can be the power generation unit 20 described above.
- a single battery 120 can be obtained by providing a positive electrode terminal and a negative electrode terminal (not shown) in such a power generation unit, and inserting the laminate using a known laminate film or the like.
- the unit cell 120 is provided with a control terminal (not shown), and the unit cell 120, 120,... Can be individually controlled by connecting the terminal to the control unit 125.
- the control unit 125 includes a control circuit and the like, and is a device that can control each of the single cells 120, 120,...
- the identification unit 150 is a unit that is inserted into the hole 135 of the exterior body 115 and identifies the presence or absence of hydrogen sulfide generation inside the exterior body 115, and includes an insertion portion 151 and a support body 155 that supports the insertion portion 151. It is comprised.
- the insertion portion 151 is a portion that is inserted from the outside of the exterior body 115 into the space 130 inside the exterior body 115 through the hole 135, and is provided so that the gas generated from the single cells 120, 120,. . At least a part of the insertion portion 151 is made of a material that changes color by chemically reacting with hydrogen sulfide, and the presence or absence of generation of hydrogen sulfide in the exterior body 115 is identified by confirming the presence or absence of the color change of the material. be able to.
- the support body 155 is a member that is fixed to the end portion of the insertion portion 151, has a size and shape that does not enter the hole 135, and in a state where the insertion portion 151 is inserted into the hole 135, the support body 155 is larger than the hole 135. It is a member that exists on the outside.
- the operator holds the support body 155 by hand, and pushes the insertion portion 151 into the hole 135 until the support body 155 is caught by the edge portion of the hole 135, thereby inserting the identification unit 150 into the exterior body 115. Can be attached to.
- the identification means 150 can be configured as shown in FIGS. As shown in FIG. 7, the insertion part 151 of the identification unit 150 includes a clamping member 153 provided with a hole 154 at least in part, and an identification part 152 provided so as to block the hole 154. .
- the sandwiching member 153 is a plate-like member for sandwiching the identification unit 152.
- the material of the sandwiching member 153 is such that the identification unit 152 can be appropriately sandwiched and is strong enough to be inserted into the hole 135.
- a resin such as polypropylene, glass, ceramics, or metal can be used.
- the thickness of the clamping member 153 is not particularly limited.
- the identification unit 152 is made of a material that changes color by reacting with hydrogen sulfide. In particular, since the color change when reacting with hydrogen sulfide is significant, among the Cu, Ni, Fe, Ag, Zn, Pb, and Mn It is preferable to consist of either.
- the identification unit 152 is preferably a film.
- the film thickness is not particularly limited as long as it is a thickness that can confirm the presence or absence of discoloration due to reaction with hydrogen sulfide.
- the end of the insertion portion 151 is fixed by a support body 155.
- the shape and material of the support 155 are not limited as long as the support 155 is strong enough to attach and detach the identification unit 150 to the exterior body 115 and can support the insertion part 151. However, as described above, the support body 155 has a size and shape that does not enter the inside of the hole 135.
- the insertion portion 151 is made of a holding member 153a provided with a hole 154a, a holding member 153b provided with a hole 154b, and a material that reacts with hydrogen sulfide and changes color.
- the film 152 identification part 152
- the insertion part 151 in which the identification part 152 is appropriately provided in the holes 154a and 154b can be manufactured.
- the identification means 150 is producible by fixing the edge part of the produced insertion part 151 to the support body 155.
- the battery 100 includes the single cells 120, 120,... Having the power generation unit including the sulfur-based material inside the outer package 115, and the holes 135 and the identification unit 150 in a part of the outer package 15. Since the identification means 150 is detachable, by confirming whether the identification means 150 is discolored, it is possible to confirm the presence or absence of hydrogen sulfide generation in the exterior body 115, and with a simple structure. The presence or absence of deterioration of the battery 100 can be identified.
- the form in which the identification unit 150 is provided in a part of the exterior body 115 has been described.
- the form of the identification unit is not limited thereto, and for example, in the first embodiment.
- the identification member 30 may be installed inside the exterior body 115, and the identification member 30 may be visible from the outside of the exterior body 115 through a viewing window.
- the battery 10 or the battery 100 When the battery 10 or the battery 100 is manufactured, for example, when the battery 10 or the battery 100 is manufactured, the presence or absence of discoloration of the identification member 30 or the identification unit 150 is confirmed visually or by an image recognition device or a reflectance measuring device. Becomes easy. In addition, even when the battery is used, the presence or absence of deterioration of the battery can be easily identified, so it is possible to easily determine whether or not battery replacement is necessary. In addition, when using the battery, the presence or absence of discoloration of the identification members 30 and 50 is monitored by an image recognition device or a reflectance measuring device, and the battery is automatically stopped when abnormality (discoloration) is detected. Thus, safety can be ensured, or the battery user can be notified promptly of the deterioration of the battery by turning on a visible lamp.
- FIG. 9 is a schematic view for explaining the structure of a battery system 200 according to a third embodiment of the present invention.
- the battery system 200 includes a battery 201 having a unit cell including a power generation unit including a sulfur-based material, the battery 201 being accommodated, and an intake port 202 and an exhaust port 203.
- a housing 204 that also functions as a fluid flow path and a duct 205 connected to the exhaust port 203 are provided.
- the casing 204 and the duct 205 can communicate with each other.
- an identification unit 250 is provided downstream of the battery 201 in the fluid flow direction.
- the battery 201 is formed by housing at least one single cell having a power generation unit including a sulfur-based material in an exterior body.
- the unit cell according to the battery 201 is not particularly limited as long as it has a power generation unit including a sulfur-based material.
- the unit cell 120 according to the second embodiment can be used.
- the material and shape of the outer package are not particularly limited as long as they can accommodate a single cell.
- at least one single cell is placed in a laminate film in which a resin film and a metal foil are laminated. Can be accommodated.
- the battery 201 in which the single cell is accommodated in the exterior body in this manner is installed inside the housing 204.
- the housing 204 has a battery 201 installed therein and an intake port 202 and an exhaust port 203. Further, a blower (not shown) is provided in the housing 204, and a fluid flow can be intentionally generated in the housing 204.
- the shape and size of the housing 204 are not particularly limited as long as the battery 201 can be appropriately installed in a shape and size.
- the material of the housing 204 is not particularly limited, and for example, a material made of a metal such as aluminum or stainless steel can be used.
- the housing 204 may be a passenger compartment provided in a part of the vehicle.
- a known fluid circulation pipe or the like may be connected to the housing 204.
- a blower or the like may be arbitrarily provided in the housing 204, and fluid intake and exhaust may be intentionally promoted.
- the duct 205 is a flow path connected to the exhaust port 203 of the housing 204, and the material, shape, and size thereof are not particularly limited.
- a fluid circulation pipe provided in the vehicle can be used as the duct 205.
- the identification unit 250 is provided at a position downstream of the battery 201 in the fluid flow direction and where the gas generated from the battery 201 can reach.
- the identification means 250 has at least a part of an identification part made of a material that changes color by reacting with hydrogen sulfide. When hydrogen sulfide is generated from the battery 201, the hydrogen sulfide comes into contact with the identification part. As a result, the identification section changes color. Therefore, by checking the presence or absence of the discoloration, it can be determined whether or not hydrogen sulfide is generated from the battery 201.
- the identification unit 250 for example, the same unit as the identification unit 150 according to the second embodiment can be used.
- the identification means 250 includes an insertion portion and a support, and the identification portion is provided in a part of the insertion portion. Then, the presence or absence of hydrogen sulfide from the battery 201 can be determined by inserting the insertion part into a position where the gas generated from the battery 201 can be reached and checking for the presence or absence of discoloration in the identification part. For example, as shown in FIG. 9, by providing a hole in a part of the duct 205 and installing the identification means 250 in the hole, when the gas generated from the battery 201 is exhausted through the duct 205, the gas is It can always be brought into contact with the identification part of the identification means 250, and when the exhausted gas contains hydrogen sulfide, the identification part changes color.
- the battery system 200 includes the battery 201 including the sulfur-based material in the housing 204 that functions as a fluid flow path, and the identification unit 250 that at least partially changes color by chemically reacting with hydrogen sulfide includes the battery Since it is provided on the downstream side in the fluid flow direction with respect to 201, the presence or absence of hydrogen sulfide generation from the battery 201 can be confirmed by confirming the presence or absence of discoloration of the identification means 250, and the battery can have a simple structure. The presence or absence of degradation of 201 can be identified.
- the form in which the identification unit 250 is provided in a part of the duct 205 has been described.
- the form of the identification unit is not limited to this, and for example, in the first embodiment.
- the identification member 30 may be installed inside the duct 205, and the identification member 30 may be visible from the outside of the duct 205 through a viewing window.
- the identification means is detachably formed like the identification means 250 (identification means 150).
- the identification unit 250 is described as being provided in a part of the duct 205, but the installation location of the identification unit 250 is not limited to this.
- the identification unit 250 may be provided on the downstream side in the fluid flow direction with respect to the battery 201 and at a position where the gas generated from the battery 201 can reach.
- the identification unit 250 is provided in the exhaust port 203 of the housing 204. May be.
- the description has been given as a mode in which a blower (not shown) is provided.
- a blower not shown
- the gas generated from the battery 201 can reach the identification unit 250, Is not necessarily required.
- a fan or the like is provided in the housing 204 from the viewpoint of intentionally generating a fluid flow in the housing 204 and reliably allowing the gas generated from the battery 201 to reach the identification unit 250. .
- the battery system 200 determines whether or not the identification means 250 has been discolored by an image recognition device, a reflectance measuring device, or the like. When monitoring is performed and an abnormality (discoloration) is detected, the battery is automatically stopped to ensure safety, or a lamp that can be seen by battery users (vehicle drivers, etc.) is lit. By doing so, it is possible to promptly notify the battery user of the deterioration of the battery.
- the installation position of the identification unit may be a position where hydrogen sulfide can be brought into contact with the power generation unit or the battery when hydrogen sulfide is generated. Since the density of hydrogen is heavier than the density of air, it is preferable to install the identification means at a position on the lower side when the battery and the battery system are used. Thereby, the detection sensitivity concerning the presence or absence of hydrogen sulfide generation can be improved.
- Example 1 A battery as shown in FIGS. 1 to 3 was fabricated and an operation test was performed.
- a transparent polyethylene film having a thickness of 50 ⁇ m was cut out to 10 ⁇ 10 mm, Cu was sputtered to a size of 2.8 ⁇ 2.8 mm on one side of the film, and an identification portion was formed on the film.
- the thickness of the identification part was about 50 nm.
- a laminate film (biaxially stretched nylon resin / aluminum foil / polyethylene resin, thickness, 20 ⁇ m / 40 ⁇ m / 50 ⁇ m) is prepared, and a 3 ⁇ 3 mm hole is formed in the exterior body so as to close the hole, The Cu deposited film was welded.
- LiCoO 2 and Li 2 S—P 2 O 5 were mixed at 1: 1 vol%, and this was coated on one side at 100 ⁇ 100 mm on a positive electrode current collector made of aluminum foil (thickness 20 ⁇ m) to form a positive electrode layer.
- a positive electrode sheet was obtained.
- graphite carbon and Li 2 S—P 2 S 5 were mixed at a ratio of 1: 1 vol%, and this was applied to a negative electrode current collector made of stainless steel foil (thickness 30 ⁇ m) on one side at 100 ⁇ 100 mm to form a negative electrode layer To form a negative electrode sheet.
- Li 2 S—P 2 S 5 was applied so as to cover the negative electrode layer, and a solid electrolyte layer was formed on the negative electrode layer. Thereafter, the positive electrode sheet and the negative electrode sheet having a solid electrolyte layer were overlapped to form a power generation unit.
- the thickness of each layer was 50 ⁇ m for the positive electrode layer, 40 ⁇ m for the solid electrolyte layer, and 70 ⁇ m for the negative electrode layer.
- a stainless steel terminal having a width of 5 mm, a length of 130 mm, and a thickness of 0.05 mm was welded to each current collector of the produced power generation unit, thereby forming a positive electrode terminal and a negative electrode terminal, respectively.
- the produced electric power generation part was accommodated in said laminate film, and the battery was produced by welding around the film.
- Example 2 A battery as shown in FIG. 4 was prepared and an operation test was performed.
- An aluminum casing (thickness: 1 mm) was prepared as an exterior body, a recess having a diameter of 15 mm and a depth of 0.5 mm was provided in a part of the exterior body, and a hole having a diameter of 3 mm was formed in the approximate center of the recess. .
- the said aluminum material with which Cu vapor deposition board was attached was inserted in the recessed part, the aluminum material and the housing
- a power generation unit having positive and negative electrode terminals was produced in the same manner as the power generation unit according to Example 1 except that the positive electrode layer or the negative electrode layer was formed on both surfaces of the current collector.
- the produced electric power generation part was accommodated in said housing
- Example 3 A plurality of batteries were installed in the casing according to Example 2, and an operation test was performed.
- Example 1 The power generation unit according to Example 1 was manufactured, and the power generation unit was accommodated in the same laminate film as that of Example 1 (however, no identification unit was provided). At this time, in order to simulate the deterioration at the time of cell destruction, a 1 cm non-welded portion was provided when welding around the laminate film.
- Battery single cells produced in this way were prepared, and each was connected in series, and then housed in the casing according to Example 2. In Example 3, the battery was produced in a glove box in an Ar atmosphere.
- Example 4 A battery as shown in FIGS. 5 to 8 (however, the control unit was omitted) was produced and an operation test was performed.
- a Cu foil having a diameter of 25 mm and a thickness of 15 ⁇ m was prepared, and this was sandwiched between two polypropylene plates (30 ⁇ 60 mm, thickness 1 mm) provided with holes 20 mm in diameter, and a support made of aluminum (40 ⁇ 20 ⁇ 4 mm) The identification means was prepared.
- An aluminum casing (thickness 1 mm) is prepared as an exterior body, a hole (2.5 ⁇ 31 mm) in which the identification means can be attached and detached is provided, and the identification means is inserted into the casing so that the identification means is attached to the casing. installed. Further, a hole was provided in a part of the housing in the same manner as in Example 2 and sealed with tape.
- Example 5 An operation test was performed using a battery system as shown in FIG. 9 (however, an identification means was installed in the vicinity of the exhaust blower provided at the exhaust port of the passenger compartment).
- the power generation unit according to Example 1 was manufactured, and the power generation unit was accommodated in the same laminate film as that of Example 1 (however, no identification unit was provided). At this time, in order to simulate deterioration at the time of cell destruction, a hole was made in the laminate film and closed with tape. Twenty batteries thus prepared were prepared and connected in series, and then housed in a pack case (thickness 1.5 mm) made of aluminum to obtain a battery (battery pack).
- the battery and battery system of the present invention are excellent in safety and reliability, and can be used in various industrial fields from a small power source such as a power source for mobile tools to a large power source such as an in-vehicle power source.
Abstract
Description
第1の本発明は、外装体内に、硫黄系材料を含む発電部と、硫化水素と化学反応することで変色する識別部と、を備え、識別部が、外装体の外部から視認可能とされている、電池である。
15 外装体
20 発電部
21 正極層
22 負極層
23 固体電解質層
24 正極集電体
25 負極集電体
26 正極端子
27 負極端子
30 識別部材(識別部)
31 透明部材(視認窓)
35 孔
36 空間
100 電池
115 外装体
120 単電池
125 制御部
130 空間
135 孔
150 識別手段
151 差し込み部
152 識別部材、膜
153 挟持部材
154 孔
155 支持体
200 電池システム
201 電池
202 吸気口
203 排気口
204 筐体(流体流通路)
205 ダクト
250 識別手段
図1~図3は本発明の第1実施形態に係る電池10の外観及び内部構造を説明するための概略図である。図1は電池10のうち、識別部として機能する識別部材30が視認される側から見た外観を、図2は、図1のII-IIに係る矢視断面を、図3は、図1のIII-IIIに係る矢視断面を概略的に示している。図2に示されるように、電池10は、外装体15の内部に、正極層21、負極層22、正極層21及び負極層22の間に設けられた固体電解質層23、正極集電体24並びに負極集電体25からなる発電部20と、正極集電体24に取り付けられた正極端子26と、負極集電体25に取り付けられた負極端子27と、を備えている。正極端子26と負極端子27とは、外装体15の内部から外部へと突出するように設けられており、これにより外部へと電気エネルギーを取り出し可能とされている。また、図3に示されるように、電池10は、外装体15の一部に孔35が設けられており、孔35の内部側には透明部材31が設けられ、透明部材31の内部側には識別部材30が設けられている。また、外装体15の内部には、空間36が存在しており、発電部20から発生した気体が、当該空間36を通って、識別部材30に到達可能とされている。以下、各構成につき説明する。
電池10の外装体15は、後述する発電部20や識別部材30を適切に収容可能なものであれば特に限定されるものではない。図1~図3においては、発電部20等は外装体15にラミネート挿入されており、すなわち外装体15としては、アルミニウム箔と樹脂フィルムとが積層されてなるラミネートフィルムが用いられている。しかしながら、外装体15はこの形態に限定されるものではなく、アルミニウム等からなる筐体を用いてもよい。外装体15の形状は、発電部20等を適切に収容可能な形態であれば特に限定されるものではない。ただし、外装体15の内部に備えられた識別部材30を視認可能とするため、外装体15には孔35が設けられている。孔35の形状や大きさについては、外装体15内部の識別部材30を視認可能であれば特に限定されるものではない。また、図3に示されるように、発電部20から発生した気体が識別部材30に到達可能なように、外装体15内には所定の空間36が設けられている。尚、当該空間36は、電池10の内部に気体が発生することにより生じた空間であってもよい。すなわち、空間36を外装体15内に予め設けておく必要はなく、電池10内部で発生した気体が、識別部材30に到達可能な形態であればよい。
発電部20は、外装体15内に収容されており、正極集電体24及び当該正極集電体24の少なくとも一面に設けられた正極層21と、負極集電体25及び当該負極集電体25の少なくとも一面に設けられた負極層22と、正極層21及び負極層22の間に設けられた固体電解質層23とを備えている。
正極層21は、正極活物質及び固体電解質を含む層であり、任意に導電助剤及び結着剤等が含まれていてもよい。電池10を全固体リチウム二次電池とする場合、活物質としては、LiCoO2、LiNiO2、Li1+xNi1/3Mn1/3Co1/3O2、LiMn2O4、Li1+xMn2-x-yMyO4(MはAl、Mg、Co、Fe、Ni、Znから選ばれる一種以上)で表される異種元素置換Li-Mnスピネル、LixTiOy、LiMPO4(MはFe、Mn、Co、Niのいずれか)、V2O5、MoO3、TiS2、グラファイト、ハードカーボン等の炭素材料、LiCoN、LixSiyOz、リチウム金属又はリチウム合金(LiM、MはSn、Si、Al、Ge、Sb、P等のいずれか)、リチウム貯蔵性金属間化合物(MgxM、MはSn、Ge、Sbのいずれか、或いは、NySb、NはIn、Cu、Mnのいずれか)や、これらの誘導体等を用いることができる。ここで、正極活物質と後述する負極活物質には明確な区別はなく、2種類の化合物の充放電電位を比較して貴な電位を示すものを正極に、卑な電位を示すものを負極に用いて、任意の電圧のリチウム二次電池を構成することができる。固体電解質としては、少なくともリチウム元素及び硫黄元素を含むものを用いる。特にLi-A-S(AはP、Ge、B、Si、及びIからなる群より選ばれる少なくとも一種)系の固体電解質を用いることが好ましく、具体的には、Li2S-P2S5、LiGe0.25P0.75S4、Li2S-B2S3、Li2S-SiS2、或いはこれらにLiIやLi2PO4等を添加したものを用いることができる。正極活物質と固体電解質の混合比は、電池10が作動可能な混合比であれば特に限定されるものではない。導電助剤としては、従来のものを特に限定されることなく用いることができ、例えば、アセチレンブラック等の炭素材料を用いることが好ましい。結着剤についても、従来のものを特に限定されることなく用いることができ、例えば、ポリフッ化ビニリデン等のフッ素樹脂やスチレンブタジエンゴム等のゴム性状樹脂等を用いることが好ましい。
正極集電体24としては、硫黄系材料を含む電池10に用いられる集電体であれば特に限定されるものではなく、例えば、金属箔や金属メッシュ、金属蒸着フィルム等を用いることができる。具体的には、Al、V、Au、Pt、Mg、Ti、Co、ステンレス鋼等の金属箔やメッシュ、或いは、ポリアミド、ポリイミド、PET、PPS、ポリプロピレンなどのフィルムやガラス、シリコン板等の上にV、Al、Pt、Au等の金属を蒸着したもの等を用いることができる。正極集電体24の厚みや大きさは特に限定されるものではない。
負極層22は、負極活物質及び固体電解質を含む層であり、任意に導電助剤及び結着剤等が含まれていてもよい。電池10を全固体リチウム二次電池とする場合に用いられる負極活物質としては上述の通りである。すなわち、上述した活物質のうち、2種類の化合物の充放電電位を比較して貴な電位を示すものを正極活物質として、卑な電位を示すものを負極活物質として用いることができる。固体電解質としては、正極層21の場合と同様、少なくともリチウム元素及び硫黄元素を含むものを用い、上述の固体電解質を用いることができる。負極活物質と固体電解質の混合比は、電池10が作動可能な混合比であれば特に限定されるものではない。導電助剤や結着剤についても、従来のものを特に限定されることなく用いることができ、上述したものを用いることができる。
負極集電体25としては、硫黄系材料を含む電池10に用いられる集電体であれば特に限定されるものではなく、例えば、金属箔や金属メッシュ、金属蒸着フィルム等を用いることができる。具体的には、ステンレス鋼、Al、V、Au、Pt、Mg、Ti、Co等の金属箔やメッシュ、或いは、ポリアミド、ポリイミド、PET、PPS、ポリプロピレンなどのフィルムやガラス、シリコン板等の上にV、Al、Pt、Au等の金属を蒸着したもの等を用いることができる。負極集電体25の厚みや大きさは特に限定されるものではない。
固体電解質層23は、正極層21及び負極層22の間に設けられる層であり、硫化物系固体電解質材料からなるものであれば特に限定されるものではない。硫化物系固体電解質材料としては、正極層21や負極層22に含まれる上記の固体電解質と同様のものを用いることができる。
正極端子26は、正極集電体24の一部(正極層21の未塗工部)に取り付けられて、発電部20で発生した電気エネルギーを外部に取り出し可能とするものである。正極端子26は、公知の金属端子を特に限定されることなく用いることができる。例えば、ステンレス鋼からなるタブを正極端子26とすることができる。正極端子26の形状や大きさは、電池10内部から外部へと電気エネルギーが取り出し可能な程度の大きさ、形状であればよく、特に限定されるものではない。正極端子26の正極集電体24への取り付けについては、特に限定されるものではないが、例えば、公知の溶接手段を用いて、溶接により正極端子26を正極集電体24に取り付け可能である。
負極端子27は、負極集電体25の一部(負極層22の未塗工部)に取り付けられて、発電部20で発生した電気エネルギーを外部に取り出し可能とするものである。負極端子27についても、正極端子26と同様に、公知の金属端子を特に限定されることなく用いることができる。例えば、ステンレス鋼からなるタブを負極端子27とすることができる。負極端子27の形状や大きさは、電池10内部から外部へと電気エネルギーが取り出し可能な程度の大きさ、形状であればよく、特に限定されるものではない。負極端子27の負極集電体25への取り付けについては、特に限定されるものではないが、例えば、公知の溶接手段を用いて、溶接により負極端子27を負極集電体25に取り付け可能である。
識別部材30は、電池10の内部(外装体15の内部)における硫化水素発生の有無を識別するための識別部として機能する部材であり、硫化水素と化学反応することで変色する材料が含まれている。当該材料としては、硫化水素と化学反応することで変色するものであれば特に限定されるものではないが、チタン、タングステン、クロム及びステンレス鋼を除いた金属や、硫化水素と反応して変色する有機化合物を用いることができる。特に、硫化水素と反応した場合の変色が顕著であることから、Cu、Ni、Fe、Ag、Zn、Pb、Mnのうちのいずれかからなる材料を用いることが好ましい。表1に、硫化水素と反応した場合の金属変色に係る具体例を示す。
透明部材31は、図3において、外装体15に設けられた孔35を塞ぐようにして、外装体15の内側に設けられる部材であり、電池10の内部を視認可能とする視認窓として機能する。透明部材31は、外装体15の外部から内部を視認可能な程度に透明なものであれば特に限定されるものではなく、ポリエチレン樹脂、アクリル樹脂、ポリプロピレン樹脂等の樹脂、ガラス、透明セラミックス等を用いることができる。透明部材31は、公知の溶着方法、接着方法や固定方法等により、外装体15の孔35部分に取り付けられる。特に、透明部材31を、ポリメタクリル酸メチル樹脂、ポリカーカーボネートやポリエチレン等からなる樹脂フィルムとすることにより、外装体15に容易に熱溶着することができるため好ましい。
図5、6は本発明の第2実施形態に係る電池100の外観及び内部構造を説明するための概略図である。図5は電池100のうち識別手段130が備えられる側から見た外観を、図6は、図5のVI-VIに係る矢視断面を概略的に示している。図6に示されるように、電池100は、外装体115を備えており、当該外装体115の内部には、硫黄系材料を含む発電部を有する単電池120、120、…と、各単電池120、120、…を制御するための制御部125とが備えられている。また、外装体115の一部には孔135が設けられており、当該孔135に、識別手段150が外装体115の外側から取り外し可能に差し込まれている。識別手段150は、差し込み部151と支持体155とを有しており、差し込み部151が外装体115の内部に突出している。また、支持体155は孔135から内部側には挿入されない程度の大きさ、形状とされており、識別手段150を容易に引き出し可能としている。外装体115の内部には空間130が設けられ、各単電池120、120、…から発生した気体は、当該空間130を通って、識別手段150の差し込み部151に到達可能とされている。
外装体115の材質、形状、大きさは、発電部120、120、…、及び制御部125を適切に収容でき、識別手段150を適切に取り付け可能なものであれば特に限定されるものではない。図5、6においては、外装体115は、アルミニウムからなる筐体とされている。また、外装体115の一部には孔135が設けられている。孔135は、識別手段150の差し込み部151を差し込み可能な程度であって、支持体155が内側に入り込まない程度の大きさ、形状とされている。
単電池120は、硫黄系材料を含む発電部を備えた単電池である。発電部としては、上述した発電部20とすることができる。このような発電部に、正極端子、負極端子(不図示)を設け、公知のラミネートフィルム等を用いてラミネート挿入することにより単電池120とすることができる。単電池120には制御用の端子(不図示)が備えられており、当該端子が制御部125に接続されることで、各単電池120、120、…を個別に制御することができる。制御部125は、制御回路等を備え、各単電池120、120、…を制御可能な装置であり、公知の制御装置等を用いることができる。
識別手段150は、外装体115の孔135に差し込まれ、外装体115内部における硫化水素発生の有無を識別するための手段であり、差し込み部151と、当該差し込み部151を支持する支持体155とを有して構成されている。
差し込み部151は、外装体115の外部から孔135を介して外装体115の内部の空間130へと差し込まれ、単電池120、120、…から発生した気体が到達可能に設けられた部分である。差し込み部151の少なくとも一部は硫化水素と化学反応することで変色する材料から構成されており、当該材料の変色の有無を確認することにより、外装体115内部における硫化水素発生の有無を識別することができる。
支持体155は、差し込み部151の端部に固定される部材であり、孔135に入り込まない程度の大きさ、形状とされ、差し込み部151が孔135に差し込まれた状態において、孔135よりも外部側に存在する部材である。外装体115内部における硫化水素発生の有無を確認するために識別手段150を外装体115から取り外す場合、作業者は、支持体155を手で持って引き出すことにより、差し込み部151を孔135から引き出すことができ、差し込み部151の変色の有無を確認することができる。また、作業者は、支持体155を手で持って、当該支持体155が孔135の縁部分に引っかかるまで、差し込み部151を孔135に押し込んで挿入することで、識別手段150を外装体115に取り付けることができる。
図9は本発明の第3実施形態に係る電池システム200の構造を説明するための概略図である。図9に示すように、電池システム200は、硫黄系材料を含む発電部を備えた単電池を有する電池201と、当該電池201が収容されるとともに、吸気口202及び排気口203を有して流体流通路としても機能する筐体204と、排気口203と接続するダクト205とを備えている。筐体204とダクト205とは、流体連通可能とされている。一方、電池201に対して流体流れ方向下流側には、識別手段250が設けられている。
電池201は、硫黄系材料を含む発電部を有する少なくとも一つの単電池を、外装体に収容してなるものである。電池201に係る単電池としては、硫黄系材料を含む発電部を有するものであれば特に限定されるものではないが、例えば、上記第2実施形態に係る単電池120とすることができる。外装体の材質、形状は、単電池を収容可能なものであれば特に限定されるものではないが、例えば、樹脂フィルム及び金属箔が積層されてなるラミネートフィルム内に、少なくとも一つの単電池を収容することができる。このように外装体内に単電池が収容されてなる電池201は、筐体204の内部に設置されている。
筐体204は、内部に電池201が設置されるとともに、吸気口202及び排気口203が備えられている。また、筐体204内には送風機(不図示)が備えられており、筐体204内において、意図的に流体流れを発生させることが可能とされている。筐体204の形状、大きさについては、電池201を適切に設置可能な形状、大きさであれば特に限定されるものではない。筐体204の材質についても、特に限定されるものではないが、例えば、アルミニウムやステンレス鋼等の金属からなるものを用いることができる。筐体204は、車両の一部に設けられた車室であってもよい。吸気口202や排気口203については、公知の流体流通管等を筐体204に接続すればよい。また、筐体204内には、任意に送風機等が備えられ、流体の吸排気を意図的に促すようにしてもよい。ダクト205は、筐体204の排気口203と接続される流通路であり、その材質や形状、大きさについては特に限定されるものではない。例えば、車両に備えられた流体流通管をダクト205とすることもできる。
識別手段250は、電池201に対して流体流れ方向下流側であって、電池201から発生した気体が到達可能な位置に設けられている。識別手段250は、少なくとも一部に硫化水素と反応して変色する材料から構成された識別部を有しており、電池201から硫化水素が発生した場合は、硫化水素が識別部と接触することにより、識別部が変色する。従って、当該変色の有無を確認することにより、電池201からの硫化水素発生の有無を判断することができる。識別手段250としては、例えば、第2実施形態に係る識別手段150と同様のものを用いることができる。すなわち、識別手段250を差し込み部と支持体とからなるものとし、差し込み部の一部に識別部を設ける。そして、差し込み部を電池201から発生した気体が到達可能な位置に差し込み、識別部の変色の有無を確認することで、電池201からの硫化水素発生の有無を判断することができる。例えば、図9に示すように、ダクト205の一部に孔を設け、当該孔に識別手段250を設置することで、ダクト205を介して電池201から発生した気体を排気する際、当該気体を識別手段250の識別部と必ず接触させることができ、排気された気体に硫化水素が含まれている場合には識別部が変色する。
図1~3に示されるような電池を作製し、作動試験を行った。
厚み50μmの透明ポリエチレンフィルムを10×10mmに切り出し、当該フィルムの片面に2.8×2.8mmのサイズにCuをスパッタし、フィルム上に識別部を形成した。識別部の厚みは50nm程度とした。
外装体として、ラミネートフィルム(2軸延伸ナイロン樹脂/アルミニウム箔/ポリエチレン樹脂、厚み、20μm/40μm/50μm)を用意し、当該外装体に3×3mmの穴を開け、穴を塞ぐようにして、上記Cu蒸着フィルムを溶着した。
LiCoO2とLi2S-P2O5を1:1vol%で混合し、これをアルミニウム箔(厚み20μm)からなる正極集電体上に、100×100mmで片面塗布して正極層を形成し、正極シートとした。また、グラファイトカーボンとLi2S-P2S5を1:1vol%で混合し、これをステンレス鋼箔(厚み30μm)からなる負極集電体上に、100×100mmで片面塗布して負極層を形成し、負極シートとした。さらに、負極層を覆うようにLi2S-P2S5を塗布し、負極層上に固体電解質層を形成した。その後、正極シートと、固体電解質層を有する負極シートとを重ね合わせて発電部とした。各層の厚みは、正極層が50μm、固体電解質層が40μm、負極層が70μmであった。作製した発電部の各集電体に、幅5mm、長さ130mm、厚み0.05mmのステンレス鋼端子を溶接し、それぞれ正極端子及び負極端子とした。
作製した発電部を上記のラミネートフィルム内に収容し、フィルムの周りを溶着して電池を作製した。
電池劣化を模擬するため、注射器を用いて150mLの空気(RL70%)をラミネートフィルム内に注入し、これを繰り返したところ、ラミネートフィルム内のCu蒸着膜が青銅色に変色したことが、電池外部から視認できた。すなわち、識別手段の変色を確認することにより、電池内における硫化水素の発生を電池外部から容易に判断することができた。
図4に示されるような電池を作製し、作動試験を行った。
直径10mm、厚み0.25mmの透明アクリル樹脂材の片面に、2.8×2.8mmのサイズにCuをスパッタし、樹脂材上に識別部を形成した。識別部の厚みは50nm程度とした。略中央に直径3.5mmの穴を有する、直径15mmのアルミニウム材(厚み0.5mm)に、作製したCu蒸着板を取り付け、後述する外装体に溶接可能な形態とした。詳細を図10に示す。
外装体として、アルミニウム製の筐体(厚み1mm)を用意し、当該外装体の一部に直径15mm、深さ0.5mmの凹部を設け、当該凹部の略中央に直径3mmの穴をあけた。Cu蒸着板が取り付けられた上記アルミニウム材を凹部に嵌め込み、アルミニウム材と筐体とを溶接し、識別手段を筐体に設置した。詳細を図10に示す。
集電体の両面に正極層、或いは負極層を形成したこと以外は、実施例1に係る発電部と同様にして正極・負極端子を有する発電部を作製した。
作製した発電部を上記の筐体内に収容し、蓋を溶接して筐体を封じた。
電池劣化を模擬するため、あらかじめ筐体に孔を設け、当該孔をテープで塞いでおいた。そこから注射器を用いて150mLの空気(RL70%)を筐体内に注入し、これを繰り返したところ、ラミネートフィルム内のCu蒸着膜が青銅色に変色したことが、電池外部から視認できた。すなわち、識別手段の変色を確認することにより、電池内における硫化水素の発生を電池外部から容易に判断することができた。
実施例2に係る筐体内に電池を複数設置し、作動試験を行った。
実施例1に係る発電部を作製し、当該発電部を実施例1と同様のラミネートフィルム(ただし、識別手段は設けていないもの)内に収容した。このとき、セル破壊時の劣化を模擬するため、ラミネートフィルムの周りを溶着する際、1cmの非溶着部を設けた。このようにして作製した電池(単電池)を4つ用意し、それぞれを直列に接続したうえで、実施例2に係る筐体内に収容した。尚、実施例3において電池の作製はAr雰囲気のグローブボックス中にて行った。
グローブボックスから作製した電池を取り出し、筐体に設けておいた孔から注射器を用いて150mLの空気(RL70%)を筐体内に注入し、これを繰り返した後、放置したところ、Cu蒸着膜が青銅色に変色していくことが電池外部から確認された。すなわち、識別手段の変色を確認することにより、電池内における硫化水素の発生を電池外部から容易に判断することができた。
図5~8に示されるような電池(ただし、制御部については省略したもの)を作製し、作動試験を行った。
直径25mm、厚み15μmのCu箔を用意し、これを直径20mmの穴が設けられたポリプロピレン板(30×60mm、厚み1mm)を2枚用いて挟み込み、アルミニウムからなる支持体(40×20×4mm)に固定し、識別手段を作製した。
外装体として、アルミニウム製の筐体(厚み1mm)を用意し、上記識別手段を着脱可能な穴(2.5×31mm)を設け、ここに識別手段を差し込むことにより、筐体に識別手段を設置した。また、筐体の一部に実施例2と同様に孔を設けテープで封じておいた。
実施例3と同様にして単電池を作製し、これを4つ直列に接続して、上記筐体内に収容し、蓋を溶接して筐体を閉じた。尚、識別手段の作製から電池の作製まで、Ar雰囲気のグローブボックス中で作業を行った。
筐体に設けておいた孔から注射器を用いて150mLの空気(RL70%)を筐体内に注入し、これを繰り返した後、放置した。その後、識別手段を筐体から取り外したところ、識別手段のCu箔が、青銅色に変色していた。すなわち、識別手段の変色を確認することにより、電池内における硫化水素の発生を電池外部から容易に判断することができた。
図9に示されるような電池システム(ただし、車室の排気口に設けられた排気ブロア近傍に識別手段を設置)を用いて、作動試験を行った。
実施例4と同様にして、識別手段を作製した。作製した識別手段は、車室の排気口に設けられた排気ブロア近傍に設置した。
実施例1に係る発電部を作製し、当該発電部を実施例1と同様のラミネートフィルム(ただし、識別手段は設けていないもの)内に収容した。このとき、セル破壊時の劣化を模擬するため、ラミネートフィルムに穴を開け、テープで閉じておいた。このようにして作製した電池を20個用意し、それぞれを直列に接続したうえで、アルミニウムからなるパックケース(厚み1.5mm)に収容し、電池(電池パック)とした。
作製した電池(電池パック)を、車室内に設置した。
電池パックの蓋を開け、中の電池につけられたテープをすばやく剥がし、即座に電池パックの蓋をし、吸気・排気動作を開始した後、識別手段を車両から取り外したところ、識別手段のCu箔が、青銅色に変色していた。すなわち、識別手段の変色を確認することにより、電池からの硫化水素発生の有無を容易に判断することができた。
Claims (7)
- 外装体内に、硫黄系材料を含む発電部と、硫化水素と化学反応することで変色する識別部と、を備え、
前記識別部が、前記外装体の外部から視認可能とされている、電池。 - 前記外装体が視認窓を備える、請求の範囲第1項に記載の電池。
- 前記識別部が、Cu、Ni、Fe、Ag、Zn、Pb及びMnのうちのいずれかを含む材料により構成されている、請求の範囲第1項又は第2項に記載の電池。
- 外装体内に、硫黄系材料を含む発電部を備え、
硫化水素と化学反応することで少なくとも一部が変色する識別手段が、前記外装体の一部に設けられている、電池。 - 前記識別手段の前記少なくとも一部が、Cu、Ni、Fe、Ag、Zn、Pb及びMnのうちのいずれかを含む材料により構成されている、請求の範囲第4項に記載の電池。
- 流体流通路内に、硫黄系材料を含む電池を備え、
硫化水素と化学反応することで少なくとも一部が変色する識別手段が、前記電池に対して流体流れ方向下流側に設けられている、電池システム。 - 前記識別手段の前記少なくとも一部が、Cu、Ni、Fe、Ag、Zn、Pb及びMnのうちのいずれかを含む材料により構成されている、請求の範囲第6項に記載の電池システム。
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DE112009000073T DE112009000073T5 (de) | 2009-11-04 | 2009-11-04 | Batterie und Batteriesystem |
CN200980101417.4A CN102119464B (zh) | 2009-11-04 | 2009-11-04 | 电池及电池系统 |
PCT/JP2009/068831 WO2011055429A1 (ja) | 2009-11-04 | 2009-11-04 | 電池及び電池システム |
KR1020107010082A KR101155755B1 (ko) | 2009-11-04 | 2009-11-04 | 전지 및 전지 시스템 |
US12/682,968 US8679664B2 (en) | 2009-11-04 | 2009-11-04 | Battery and battery system |
JP2010506472A JP5533647B2 (ja) | 2009-11-04 | 2009-11-04 | 電池及び電池システム |
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JP2018018817A (ja) * | 2016-07-19 | 2018-02-01 | パナソニックIpマネジメント株式会社 | 電池 |
JP2018073802A (ja) * | 2016-04-25 | 2018-05-10 | パナソニックIpマネジメント株式会社 | 電池、および、電池システム |
JP2020017485A (ja) * | 2018-07-27 | 2020-01-30 | トヨタ自動車株式会社 | 全固体電池 |
WO2021172004A1 (ja) * | 2020-02-25 | 2021-09-02 | 凸版印刷株式会社 | 全固体電池用外装材及びこれを用いた全固体電池 |
JP2021174697A (ja) * | 2020-04-27 | 2021-11-01 | 凸版印刷株式会社 | 蓄電装置用端子フィルム及び蓄電装置 |
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CN102119464A (zh) | 2011-07-06 |
KR101155755B1 (ko) | 2012-06-12 |
DE112009000073T5 (de) | 2012-12-06 |
CN102119464B (zh) | 2015-07-29 |
JPWO2011055429A1 (ja) | 2013-03-21 |
KR20110070836A (ko) | 2011-06-24 |
US8679664B2 (en) | 2014-03-25 |
US20120015220A1 (en) | 2012-01-19 |
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