WO2011148631A1 - 固体電解質二次電池 - Google Patents
固体電解質二次電池 Download PDFInfo
- Publication number
- WO2011148631A1 WO2011148631A1 PCT/JP2011/002914 JP2011002914W WO2011148631A1 WO 2011148631 A1 WO2011148631 A1 WO 2011148631A1 JP 2011002914 W JP2011002914 W JP 2011002914W WO 2011148631 A1 WO2011148631 A1 WO 2011148631A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- negative electrode
- positive electrode
- active material
- solid electrolyte
- electrode active
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
- 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
- H01M10/38—Construction or manufacture
-
- 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
- H01M10/3918—Sodium-sulfur cells characterised by the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2200/00—Safety devices for primary or secondary batteries
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a secondary battery using a solid electrolyte such as ⁇ alumina.
- a conventional general sodium-sulfur battery has a bottomed cylindrical solid electrolyte made of a material such as ⁇ -alumina that is permeable to sodium ions, and a cylindrical case that holds this solid electrolyte in the axial center portion, It is comprised from the molten sodium accommodated in the cathode chamber provided inside the solid electrolyte, and the molten sulfur accommodated in the anode chamber provided inside the case and outside the solid electrolyte.
- This sodium-sulfur battery is heated to an operating temperature of 290 to 350 ° C., and molten sodium in the cathode chamber becomes sodium ions, permeates the solid electrolyte, reacts with sulfur in the anode chamber, and produces sodium polysulfide. It is generated and discharged. At the time of charging, the reverse reaction proceeds and molten sodium is returned to the cathode chamber.
- the solid electrolyte of this sodium-sulfur battery is formed of ⁇ alumina or ⁇ "alumina made of sodium oxide and aluminum oxide, and has a bottomed cylindrical shape, that is, a test tube shape.
- Japanese Patent Laid-Open No. 2-112168 uses a cathode container having a small hole in the bottom in a cathode chamber of a bottomed cylindrical solid electrolyte, and further includes a solid electrolyte partition wall.
- a safety tube is used between the peripheral surface side and the outer peripheral surface side of the cathode container.
- JP-A-50-38030 discloses a plate-shaped solid electrolyte.
- This plate-like solid electrolyte has a shape in which a plurality of independent pores are provided downward from the center in the thickness direction of the plate-like upper end surface.
- Molten sodium is stored in a sodium storage container at a position apart from the solid electrolyte, and sodium is supplied from the storage container to the pores provided in the plate-shaped solid electrolyte. Even if this plate-like solid electrolyte is damaged and molten sodium flows out, the amount of molten sodium in the pores is small, so that it does not become a big problem.
- the plate-shaped solid electrolyte is not easy to mold, it is not suitable for mass production, and there is a problem that the battery cost per unit cell becomes high.
- the conventional sodium-sulfur battery has a configuration in which a solid electrolyte is accommodated in a central portion of a metal positive electrode container that accommodates molten sulfur.
- the sodium-sulfur battery is a high-temperature battery that operates at 290 to 350 degrees as described above, and the temperature change due to repeated operation and stop is large.
- the thermal stress based on the difference in expansion and contraction of the outer cylinder container and ⁇ -alumina due to temperature change and mechanical stress based on external force are likely to be applied to the joint. For this reason, there is a risk that cracks may occur in the joint or may be damaged.
- the solid electrolyte is formed thin in order to improve sodium ion conductivity, sufficient strength cannot always be obtained. For this reason, the stress due to the temperature change is applied, so that the solid electrolyte is damaged, and further, the active material may leak to the outside of the battery.
- Various improvements have been made correspondingly (Japanese Patent Laid-Open Nos. 3-187160 and 6-196204).
- Japanese Patent Laid-Open No. 2-112168 JP 50-38030 A Japanese Patent Laid-Open No. 3-187160 JP-A-6-196204 JP 2001-93570 A Japanese Patent Laid-Open No. 2001-102877 JP 2001-243975 A Japanese Unexamined Patent Publication No. 7-176328 Japanese Patent Laid-Open No. 11-121031 Japanese Patent Laid-Open No. 10-302830 JP-A-63-271865 JP-A 63-66863
- the first object of the present invention is to provide a solid electrolyte secondary battery having a structure that can provide further safety.
- the second object of the present invention is to provide a solid electrolyte secondary battery having a simpler structure.
- it is a third object to provide a solid electrolyte secondary battery that is energized in the direction in which the crack is closed, in which the crack gap does not widen even if a crack occurs in the solid electrolyte.
- a fourth object is to provide a solid electrolyte secondary battery in which the active material does not leak outside the battery even if the solid electrolyte is damaged. It is a longitudinal cross-sectional view.
- the solid electrolyte secondary battery of the present invention includes a negative electrode active material, a positive electrode active material, a negative electrode active material storage container that stores a part of the negative electrode active material, and at least a part of a positive electrode chamber that holds the positive electrode active material. And a positive electrode active material formed separately from the negative electrode active material storage container, with a solid electrolyte that partitions the negative electrode active material and at least a part of the negative electrode chamber that holds the other part of the negative electrode active material And a storage container.
- the negative electrode active material storage container and the positive electrode active material storage container are formed separately, some of the negative electrode active material and the positive electrode active material chamber are separated into different containers.
- the negative electrode active material is a metal typified by sodium, and lithium, potassium and the like are also candidates.
- the positive electrode active material include sulfur or a mixture of sulfur and molten salt (sodium chloride and aluminum chloride).
- the positive electrode active material refers to a material that reacts with the negative electrode active material to form a compound.
- the solid electrolyte refers to a ceramic that allows a cathode active material such as ⁇ -alumina and ⁇ “alumina to pass therethrough.
- the negative electrode active material storage container of the present invention stores the remaining negative electrode active material other than that held in the negative electrode chamber, and a large part of the negative electrode active material is stored in the negative electrode active material storage container.
- the portion of the negative electrode active material and the positive electrode active material can be moved away from each other, increasing safety. Further, at the time of discharging, since the negative electrode active material can be supplied from the negative electrode active material storage container to the negative electrode chamber by the amount of the negative electrode active material reduced by the discharge reaction, the amount of negative electrode active material that can be stored in the negative electrode chamber Even if there is little, battery capacity is not reduced.
- the negative electrode active material storage container is formed of a material having corrosion resistance to the negative electrode active material, preferably a metal material having corrosion resistance.
- the shape of the negative electrode active material storage container is not limited to a specific one as long as it functions as a container.
- the positive electrode active material storage container of the present invention is a portion formed of a solid electrolyte that partitions at least a part of a positive electrode chamber holding a positive electrode active material and at least a part of a negative electrode chamber holding a part of the negative electrode active material. Is a container with Even if the entire container is formed of a solid electrolyte, a portion that does not contribute to the battery reaction may be formed of a substance other than the solid electrolyte. In other words, in the present invention, the positive electrode chamber itself formed mainly of a solid electrolyte is used as a container for the positive electrode active material.
- the positive electrode active material storage container of the present invention may have at least one positive electrode chamber and a plurality of negative electrode chambers that are separated from the wall surface along a wall surface that defines the positive electrode chamber. . More specifically, both the positive electrode chamber and the negative electrode chamber can have a hole shape (cylinder shape) extending in the axial direction.
- the positive electrode active material storage container can have a columnar outer shape.
- the column shape means a shape extending in a uniaxial direction.
- the outer peripheral shape can be an arbitrary shape such as a circle, an ellipse, a triangle, or a quadrangle.
- the column shape referred to in the secondary battery of the present invention has at least one positive electrode chamber extending in the axial direction.
- the cross-sectional shape of the positive electrode chamber can be any shape such as a circle, an ellipse, a triangle, and a quadrangle.
- the positive electrode active material storage container having this column shape is simple in shape and easy to manufacture because it extends in the axial direction.
- the negative electrode chamber extends in the axial direction along the wall surface of the positive electrode chamber and is spaced from the wall surface, and the cross section can be formed as a space having a smaller area than the cross section of the positive electrode chamber. Specifically, a plurality of negative electrode chambers are formed around the positive electrode chamber. A gap portion between the negative electrode chamber and the positive electrode chamber mainly functions as an electrolyte. When the positive electrode active material in the positive electrode chamber and the negative electrode active material in the negative electrode chamber are connected by an external circuit, the single cell functions.
- the solid electrolyte secondary battery of the present invention may have a biasing member that abuts at least a part of the outer surface of the positive electrode active material storage container and biases the positive electrode active material storage container toward the center.
- This urging member can be made of, for example, a heat-resistant carbon fiber, glass fiber or the like compressed or formed into a thin mat shape.
- the container-shaped body before the crack is generated can be maintained, and leakage of the positive electrode active material from the crack can be suppressed. Therefore, by providing the urging member, the generation of cracks in the positive electrode active material container can be suppressed, and mixing of the negative electrode active material and the positive electrode active material can be prevented.
- biasing member examples include a band. The force tightened by the band is used as the biasing force.
- the positive electrode active material storage container of the present invention includes a cylindrical container body formed of a solid electrolyte that partitions a positive electrode chamber therein, and a negative electrode that covers the outer peripheral surface of the container main body and forms a negative electrode chamber between the outer peripheral surface. It can consist of a member.
- the solid electrolyte constitutes a cylindrical container body. And the positive electrode chamber in which a positive electrode active material is accommodated inside this container main body is formed. Further, the negative electrode member covers the outer surface of the container body, and a gap formed by the outer peripheral surface of the container body and the inner surface of the negative electrode member is a negative electrode chamber in which the negative electrode active material is accommodated. That is, since the negative electrode chamber is formed as a gap between the container main body and the negative electrode member, the amount of highly active negative electrode active material present in the negative electrode chamber is small, and the container main body composed of a solid electrolyte should be damaged. The negative electrode active material that leaks out is also less safe. Further, by forming the negative electrode chamber over almost the entire region of the outer surface of the container body, a large area that functions as a partition wall for the solid electrolyte can be secured, and the output of the battery can be increased.
- the container body has a cylindrical shape, and a space defined by the inner surface of the container body serves as a positive electrode chamber and a space for containing a positive electrode active material active material.
- the cross-sectional shape of the container body can be an arbitrary shape such as a circle, an ellipse, a triangle, or a quadrangle.
- the positive electrode chamber extends in the axial direction, and the cross-sectional shape thereof is circular or elliptical. , A triangle, a quadrangle, etc.
- this container body extends in the axial direction, it has a simple shape and is easy to manufacture.
- the negative electrode chamber is a space defined by the outer surface of the container body and the inner surface of the negative electrode member disposed on the outer surface of the container body. Accordingly, the negative electrode chamber extends in the axial direction and is formed so as to surround the periphery of the positive electrode chamber with a container body made of a solid electrolyte therebetween.
- the cross-sectional shape of the negative electrode chamber can be any shape such as a circular, elliptical, triangular, or quadrangular ring depending on the shape of the container body and the shape of the negative electrode member disposed around the container body.
- the amount of the negative electrode active material accommodated can be reduced when the space formed by the outer surface of the container body and the inner surface of the negative electrode member is made as narrow as possible, the safety is increased.
- the negative electrode member preferably has protrusions extending in the axial direction toward the inner surface side and having tips that press the outer peripheral surface of the container body at predetermined intervals.
- the negative electrode member can be formed of a metal such as stainless steel or aluminum.
- the protrusion may be any protrusion that protrudes at least from the inner surface side of the negative electrode member and extends along the outer surface of the container body. Therefore, for example, the negative electrode member may be provided with protrusions at predetermined intervals on the inner surface of a flat plate. Further, the negative electrode member may be bent in a wave shape at a predetermined interval so that the protrusions are continuously arranged on both the outer side surface and the inner side surface of the negative electrode member.
- the negative electrode member when the metal is formed into a plate shape, the negative electrode member is covered so as to wind the plate-shaped negative electrode member along the outer peripheral surface direction of the container body.
- the length of the plate-like negative electrode member in the longitudinal direction is formed shorter than the length of the outer periphery of the container body. And it joins and closes in the state which pulled both ends of the plate-shaped negative electrode member wound along the outer peripheral surface direction.
- the tips of the plurality of protrusions formed on the inner surface of the negative electrode member come into contact with the outer peripheral surface of the container main body, and the protrusions press the outer peripheral surface of the container main body toward the center side, that is, the axial center. .
- the container body is pressed axially from the outside of the container body and further axially from both ends of the container body due to a pressure difference with the atmosphere.
- the container body is pressed in the direction in which the shape is reduced, that is, in the direction in which the circumference is reduced and the axial length is reduced.
- the force of the press is pressed down in the direction which closes a crack part. Therefore, the shape of the container body before the crack is generated can be maintained, and leakage of the negative electrode active material through the crack can be suppressed.
- the positive electrode active material accommodating space is a shape extending in a uniaxial direction.
- the outer peripheral shape of the container body can be an arbitrary shape such as a circle, an ellipse, a triangle, or a rectangle.
- the positive electrode chamber extends in the axial direction, and the cross-sectional shape thereof is circular or elliptical. , A triangle, a quadrangle, etc.
- the negative electrode member preferably has protrusions extending in the axial direction toward the inner surface side and having tips that press the outer peripheral surface of the container body at predetermined intervals. Moreover, it is preferable that a negative electrode member shall have a wavy part extended along the outer peripheral surface of a container main body. Furthermore, the negative electrode chamber can be provided with a porous spacer to hold the negative electrode active material in the hole of the spacer.
- the solid electrolyte secondary battery may have a biasing member that biases the container body of the positive electrode active material storage container toward the center.
- the biasing member can be provided between the inner surface side of the negative electrode member and the outer surface side of the container body, that is, in the negative electrode chamber.
- This urging member can be made into a thinner mat by compressing, for example, heat-resistant carbon fiber or glass fiber.
- the biasing member is disposed between the inner surface side of the negative electrode member and the outer surface side of the container main body, and abuts against at least a part of the outer surface of the container main body, so that the container main body is directed toward the center side, that is, toward the axis. And press elastically. Further, since the positive electrode chamber is sealed under reduced pressure, the container body is pressed axially from the outside of the container body and further axially from both ends of the container body due to a pressure difference with the atmosphere.
- the container body is pressed in the direction in which the shape is reduced, that is, in the direction in which the circumference is reduced and the axial length is reduced. For this reason, even if the container body is broken and cracked, the pressing force presses the cracked portion in the closing direction. Therefore, the shape of the container body before the crack is generated can be maintained, and leakage of the negative electrode active material from the crack can be suppressed. Therefore, by providing the urging member, generation of cracks in the container body can be suppressed, and mixing of the negative electrode active material and the positive electrode active material can be prevented.
- the positive electrode active material storage container of the present invention may have a cylindrical container body formed of a solid electrolyte, and ceramic top and bottom lids fixed to the upper and lower sides, respectively. Furthermore, the positive electrode active material storage container of the present invention can have a soft sheet that hermetically covers the outer peripheral surface thereof.
- a negative electrode active material storage container for storing a negative electrode active material and a positive electrode active material storage container for storing a positive electrode active material are separately provided.
- the container for storing the negative electrode active material and the positive electrode active material is integrally provided in one single cell, the structure for sealing is complicated.
- the sealing structure can be simplified and the operation cost can be kept low.
- a positive electrode active material storage container in which a positive electrode chamber is formed inside a container main body made of a cylindrical solid electrolyte and a negative electrode chamber is formed inside or outside the container main body has a ceramic upper lid and a bottom lid made of a solid electrolyte.
- the container body is hermetically sealed by being fixed to the upper side and the lower side, respectively.
- a fixing method for example, glass bonding, brazing, thermal diffusion bonding, or the like can be considered.
- the solid electrolyte is made of ⁇ -alumina or the like, the container body made of the solid electrolyte, the top lid and the bottom lid are joined between ceramics, and can be joined more easily than when metal and ceramic are joined. It becomes possible.
- the ceramic forming the top lid and the bottom lid for example, ⁇ -alumina, ⁇ alumina, ⁇ ′′ alumina, silicon carbide, silicon nitride, or the like can be used.
- the outer peripheral surface of the positive electrode active material storage container is hermetically covered with a soft sheet to provide a structure having higher sealing performance.
- the soft sheet seals the positive electrode active material storage container from the outside. Since it is housed, there is no risk of the active material leaking outside, and a highly safe solid electrolyte secondary battery can be realized.
- the negative electrode chamber may be formed in a container main body formed of a solid electrolyte spaced apart from the positive electrode chamber, and may include a plurality of holes extending in the axial direction and formed in the circumferential direction. That is, a plurality of hole-like spaces that are formed so as to surround the positive electrode chamber along the inner wall surface of the cylindrical container main body that partitions the positive electrode chamber, and that extend in the axial direction inside the peripheral wall of the container main body become the negative electrode chamber. .
- the outer surface of the cylindrical container body can be covered with a negative electrode member, and the gap formed by the outer surface of the container body and the inner surface of the negative electrode member can be used as the negative electrode chamber.
- a negative electrode member for example, a plate made of a metal such as stainless steel or aluminum can be used.
- the soft sheet is made of a metal foil.
- the positive electrode active material storage container can be hermetically stored relatively easily without being restricted by the size and shape of the positive electrode active material storage container, and the material cost is low.
- the material of the metal foil is required to be easily welded, have good rust resistance, high heat resistance, and high mechanical strength.
- the material for example, aluminum, copper, nickel, iron, titanium, stainless steel or the like can be used.
- required above is used suitably.
- an anode rod extending in the axial direction in the cathode chamber having one end fixed to the upper lid or the bottom lid can be provided in the cathode active material storage container. Further, among the anode rods, those having plate-like spacing pieces extending radially in the radial direction and forming the positive electrode chamber in a plurality of sections can be used. Thereby, since the reaction area of the battery in the positive electrode chamber can be increased, the efficiency of the charge / discharge reaction can be increased.
- the solid electrolyte secondary battery may include a porous spacer that exerts a pressure acting on the outer surface of the negative electrode member on the outer peripheral surface of the container body formed of the solid electrolyte.
- the pressure acting on the outer surface of the negative electrode member is transmitted to the outer peripheral surface of the container body through the porous spacer held in the negative electrode chamber, and acts as a force for compressing the container body. For this reason, even if the container body is damaged and a crack is generated, the compressing force is pressed down in the direction of closing the crack portion. Therefore, the shape of the container body before the crack is generated can be maintained, and the leakage of the active material from the crack can be suppressed.
- porous material constituting the porous spacer for example, metal fiber, foam metal, porous ceramic or the like can be used.
- the porous spacer is held in the negative electrode chamber and impregnated with a negative electrode active material such as molten sodium.
- FIG. 1 is a longitudinal sectional view of a sodium sulfur battery of Example 1.
- FIG. 1 is a cross-sectional view of a sodium sulfur battery of Example 1.
- FIG. 1 is a perspective view of a container body that is a columnar body of a solid electrolyte used in a sodium-sulfur battery of Example 1.
- FIG. 4 is a cross-sectional view of a sodium sulfur battery of Example 2.
- FIG. 6 is a cross-sectional view of a sodium-sulfur battery of Example 3.
- FIG. 6 is a cross-sectional view of a sodium-sulfur battery of Example 4.
- FIG. 6 is a cross-sectional view of a sodium sulfur battery of Example 5.
- FIG. 6 is a cross-sectional view of a sodium sulfur battery of Example 6.
- FIG. 6 is a cross-sectional view of a sodium sulfur battery of Example 7.
- FIG. 10 is a longitudinal sectional view of a sodium-sulfur battery of Example 8.
- FIG. 10 is a transverse cross-sectional view of a sodium sulfur battery of Example 8.
- FIG. 10 is a partially enlarged view of a cross-sectional view of the sodium sulfur battery of Example 8.
- FIG. 10 is a cross-sectional view of a main part of a modification of Example 8.
- FIG. 14 is a partially enlarged view of FIG. 13.
- FIG. 10 is a transverse cross-sectional view of another modification of Example 8.
- FIG. 14 is a partially enlarged view of FIG. 13.
- FIG. 10 is a longitudinal sectional view of another modification of Example 8.
- 10 is a longitudinal sectional view of another modification of Example 8.
- 10 is a longitudinal sectional view of a sodium-sulfur battery of Example 9.
- FIG. 10 is a cross-sectional view of the sodium sulfur battery of Example 9.
- 10
- FIG. 1 is a longitudinal sectional view of a sodium-sulfur battery 1 of Example 1 of the present invention
- FIG. 2 is a transverse sectional view of an essential part thereof
- the sodium-sulfur battery 1 includes a metallic cylindrical protective can 11, a sodium container 13 held on an upper portion in the space of the protective can 11 via an insulator 12 formed of a glass fiber mat, Molten sodium 14 held in the sodium container 13, a cylindrical container body 15 made of ⁇ -alumina held in the lower part of the space of the protective can 11, and molten sulfur held in this internal space 16 and a biasing member 17 made of a carbon fiber mat disposed in a compressed state between the outer peripheral surface of the container body 15 and the inner peripheral surface of the protective can 11 is a main component. As shown in FIG. 3, the container main body 15 has a thick cylindrical shape, and the internal space corresponding to the shaft hole becomes the positive electrode chamber 18.
- the container body 15 is manufactured by a known method in which a rod-shaped molded body is obtained by ceramic extrusion molding, cut into a predetermined length, heated to perform a degreasing process for removing a binder such as a resin, and then sintered. it can.
- the container body 15 can also be made by machining a block-shaped compact body obtained by compacting a powdered solid electrolyte into a predetermined shape and then sintering it.
- An upper lid 151 made of ⁇ -alumina is integrally bonded and fixed to the upper end surface of the container body 15 with a glass adhesive or the like.
- the upper lid 151 has a ring-shaped groove on its lower surface, and the opening surface of the groove is closed by the upper end surface of the container body 15 to form a ring-shaped passage 152.
- This ring-shaped passage 152 communicates with the upper end openings of all the negative electrode chambers 19 of the container body 15.
- a vertical passage 153 extending from the upper surface of the upper lid 151 to the ring-shaped passage 152 is provided.
- a sealing ring 155 made of ⁇ -alumina is integrally bonded and fixed to the lower end surface of the container body 15 with a glass adhesive or the like.
- the sealing ring 155 functions to seal the lower end opening of the negative electrode chamber 19 provided at equal intervals in the circumferential direction of the container body 15.
- the sodium storage container 13 is disposed on the upper lid 151.
- a through hole is formed in the bottom of the sodium storage container 13, and a metal connecting pipe 154 having an axial hole is inserted and joined to the through hole and a vertical passage 153 that is a common hole with the through hole. .
- Molten sodium 14 is held in the sodium container 13, and the molten sodium 14 passes through the shaft hole of the connecting pipe 154, the vertical passage 153, and the ring-shaped passage 152, flows into all the negative electrode chambers 19, and fills the negative electrode chamber 19. It will be. Further, as shown in FIG.
- a biasing member 17 made of a carbon fiber mat is compressed between the outer peripheral surface of the container main body 15 and the inner peripheral surface of the protective can 11 in the thickness direction. It is stored in the can 11.
- a current collector 20 made of a carbon fiber aggregate impregnated with sulfur 16 as a positive electrode active material is inserted into the positive electrode chamber 18 formed in the container body 15. Further, a metal anode rod 21 is provided at the central portion of the current collector 20.
- a metal bottom lid 111 is joined to the lower end surface of the container body 15 with a glass adhesive, and the positive electrode chamber 18 is formed as a closed space. The bottom lid 111 is welded to the side peripheral portion of the protective can 11 and becomes the bottom of the protective can 11.
- the anode rod 21 is joined to the bottom lid 111. Further, a cathode terminal 22 is joined to the sodium storage container 13, and an upper portion thereof protrudes upward through a through hole of the protective can 11. Further, an anode terminal 23 is joined to the upper side of the protective can 11.
- the sodium-sulfur battery 1 of Example 1 has the above-described configuration. The sodium-sulfur battery 1 is used after being heated to a temperature of 300 ° C. to 350 ° C. At the time of discharge, the molten sodium 14 in the negative electrode chamber 18 becomes sodium ions, passes through the portion of the container body 15 that becomes the partition wall of the solid electrolyte, moves to the positive electrode chamber 18, contacts and reacts with the molten sulfur 16, and discharges sodium sulfide.
- this sodium sulfur battery 1 has the positive electrode chamber 18 and the negative electrode chamber 19 inside the container body 15, the structure is very simple compared to a conventional sodium sulfur battery, and the number of parts constituting the battery can be reduced. it can. Moreover, since the negative electrode chamber 19 is formed in a pore shape and has a small volume per chamber, the amount of molten sodium 14 accommodated can be reduced. Since most of the molten sodium 14 is held in a sodium storage container 13 that is provided separately from the positive electrode chamber 18, most of the molten sodium 14 and molten sulfur 16 can be kept away from each other. Increase.
- the molten sodium 14 is divided and accommodated in the plurality of negative electrode chambers 19, even if the container body 15 is broken, the amount of the molten sodium 14 that reacts directly with the molten sulfur 16 can be suppressed. Further, although the amount of molten sodium 14 stored in the negative electrode chamber 19 is small, as described above, since the molten sodium 14 is replenished from the sodium storage container 13, a constant amount of molten sodium is always stored in the negative electrode chamber 19. Sodium 14 can be stored. Therefore, the problem that the molten sodium 14 is insufficient and the battery capacity is reduced does not occur. Further, the urging member 17 is disposed in a compressed state between the outer peripheral surface of the container main body 15 and the inner peripheral surface of the protective can 11.
- the urging member 17 elastically presses the container body 15 toward the center side by the repulsive force of the compression. Therefore, even if the container main body 15 is broken and a crack is generated, the pressure is pressed in the direction of closing the crack portion. Therefore, the shape of the container main body 15 before a crack arises can be maintained, and it can suppress that the molten sodium 14 leaks from a crack.
- the shape of the container main body 15 is not restricted to what was shown in Example 1, Various shapes can be considered. Cross-sectional views of a sodium sulfur battery having a container body having a shape different from that of Example 1 are shown in FIGS.
- container bodies having different shapes will be described with reference to FIGS. 4 to 9, the molten sulfur, the current collector and the anode rod are not shown.
- FIG. 4 shows a cross-sectional view of the main part of the sodium-sulfur battery of Example 2 of the present invention.
- the sodium-sulfur battery of this example is different in the shape of the positive electrode active material storage container constituting the sodium-sulfur battery of Example 1, particularly the container body.
- the other components are almost the same as those of the first embodiment, so that the description thereof is omitted.
- the container body 25 of the sodium-sulfur battery of Example 2 has a columnar shape in which the outer peripheral shape extends in the axial direction like the container body 15 shown in FIG. 2 of Example 1.
- the container body 25 is housed in a metal cylindrical protective can 11, and the urging member 17 is disposed between the outer peripheral surface of the container main body 25 and the inner peripheral surface of the protective can 11. As shown in FIG.
- Each positive electrode chamber 28 has a hole shape extending in the axial direction having a circular cross section.
- a large number of negative electrode chambers 29 are formed at equal intervals in the circumferential direction along the wall surfaces of the three positive electrode chambers 28 with a slight gap therebetween.
- the negative electrode chamber 29 has a pore shape extending in the axial direction.
- the area which becomes the partition wall of the solid electrolyte can be increased, and more sodium ions can permeate and react with the electrolyte. Further, since some of the negative electrode chambers 29 are also used as the adjacent positive electrode chambers 28, more sodium ions can permeate through the electrolyte and react. Therefore, the battery output per unit cell can be raised by making the container main body 25 into such a shape.
- FIG. 5 shows a cross-sectional view of the main part of the sodium-sulfur battery of Example 3 of the present invention.
- the sodium-sulfur battery of this example is different in the shape of the positive electrode active material storage container constituting the sodium-sulfur battery of Example 1, particularly the container body.
- the other components are almost the same as those of the first embodiment, so that the description thereof is omitted.
- the container main body 35 has a columnar shape whose outer peripheral shape extends in a circular axial direction.
- the container body 35 is housed in a metallic cylindrical protective can 11, and the urging member 17 is disposed between the outer peripheral surface of the container main body 35 and the inner peripheral surface of the protective can 11.
- Seven positive electrode chambers 38 are formed inside the container body 35.
- Each positive electrode chamber 38 has a hole shape extending in the axial direction having a circular cross section.
- a large number of negative electrode chambers 39 are formed at equal intervals in the circumferential direction along the wall surfaces of the seven positive electrode chambers 38 with a slight gap therebetween.
- the negative electrode chamber 39 has a pore shape extending in the axial direction.
- the battery output per unit cell can be further increased by forming the container body 35 in such a shape.
- FIG. 6 shows a cross-sectional view of the main part of the sodium-sulfur battery of Example 4 of the present invention.
- the container body 45 of the sodium-sulfur battery of this embodiment has a columnar shape in which the outer peripheral shape extends in the axial direction like the container body 15 of FIG.
- the container body 45 is housed in a metal cylindrical protective can 11, and the urging member 17 is disposed between the outer peripheral surface of the container main body 45 and the inner peripheral surface of the protective can 11.
- 19 positive electrode chambers 48 are formed inside the container body 45.
- the positive electrode chamber 48 has a hole shape extending in the axial direction having a circular cross section.
- a large number of negative electrode chambers 49 are formed at equal intervals in the circumferential direction along the wall surfaces of the nineteen positive electrode chambers 48 with a slight gap therebetween.
- the negative electrode chamber 49 has a pore shape extending in the axial direction.
- FIG. 7 shows a cross-sectional view of the main part of the sodium-sulfur battery of Example 5 of the present invention.
- the container body 55 of the sodium-sulfur battery of this embodiment has a columnar shape in which the outer peripheral shape extends in the axial direction like the container body 15 of FIG.
- the container body 55 is housed in a metal cylindrical protective can 11, and the urging member 17 is disposed between the outer peripheral surface of the container main body 55 and the inner peripheral surface of the protective can 11.
- one hole-like positive electrode chamber 58 extending in the axial direction having a substantially circular cross section is formed inside the container body 55.
- the positive electrode chamber 58 has semicircular convex portions at regular intervals on the entire peripheral surface thereof.
- a large number of negative substance storage chambers 59 are formed on the entire peripheral surface at a position surrounded by the wall surface of the semicircular convex portion and with a slight gap from the wall surface.
- the negative electrode chamber 59 has a pore shape extending in the axial direction. By making the container main body 55 into such a shape, the number of negative electrode chambers 59 that can be formed inside is reduced. However, by enclosing the negative electrode chamber 59 with the wall surface of the semicircular convex portion, it is possible to increase the area to be a partition wall of the solid electrolyte. Therefore, the output of the battery per unit cell can be increased. Further, since the volume of the positive electrode chamber 58 can be increased as much as the number of the negative electrode chambers 59 is reduced, a larger amount of molten sulfur can be accommodated. Therefore, the battery capacity per unit cell can be increased.
- FIG. 8 shows a cross-sectional view of the main part of the sodium sulfur battery of Example 6 of the present invention.
- the container body 55 of the sodium-sulfur battery of this embodiment is a columnar shape whose outer peripheral shape extends in the axial direction of a square, unlike the container body 15 of FIG.
- the container main body 65 is accommodated in a metal cylindrical protective can 61 having a rectangular outer peripheral shape, and a biasing member 67 is disposed between the outer peripheral surface of the container main body 65 and the inner peripheral surface of the protective can 61.
- the positive electrode chamber 68 has a hole shape extending in the axial direction having a quadrangular cross section.
- the negative electrode chambers 69 are continuously formed at regular intervals along the wall surfaces of the four positive electrode chambers 68 with a slight gap from the wall surfaces.
- the negative electrode chamber 69 has a hole shape extending in the axial direction having a rectangular cross section.
- an urging member 67 made of a carbon fiber mat is accommodated in a compressed state with high density at the four apex portions of the container body 65 having a square cross section. Further, the biasing member 67 is stored in a state of being gradually compressed to a low density along one side of the container main body 65 from one apex, and is gradually compressed to a high density as approaching the other apex. It is stored in. By disposing the urging member 67 in this way, it becomes possible to press more strongly and elastically than the other outer peripheral surfaces from the four vertex directions toward the center of the container main body 65.
- the polygonal apex portion is more resistant to external pressure than other portions, it is possible to pressurize the entire outer peripheral surface in a balanced manner by changing the pressing force for each portion. By doing in this way, it becomes possible to press down in the direction which closes a crack part, and the shape of the container main body 65 can be maintained.
- FIG. 9 shows a cross-sectional view of the main part of the sodium-sulfur battery of Example 7 of the present invention.
- the container body 55 of the sodium-sulfur battery of this embodiment is a columnar shape whose outer peripheral shape extends in the axial direction of a hexagon, unlike the container body 15 of FIG.
- the container body 75 is housed in a metal cylindrical protective can 71 having an outer peripheral shape of hexagonal shape, and a biasing member 77 is disposed between the outer peripheral surface of the container main body 75 and the inner peripheral surface of the protective can 71.
- the Inside the container body 75 six hole-shaped positive substance storage chambers 78 extending in the axial direction having a triangular cross section are formed so that the apex of the triangle is the center and the base is parallel to the hexagonal side.
- a large number of negative electrode chambers 79 are formed at regular intervals along the wall surfaces of the six positive electrode chambers 78 and with a slight gap from these wall surfaces.
- the negative electrode chamber 79 has a hole shape extending in the axial direction having a rectangular cross section.
- a biasing member 77 made of a carbon fiber mat is accommodated in a compressed state with high density at the six apex portions of the container body 75 having a hexagonal cross section. Further, the biasing member 77 is housed in a state where it is gradually compressed to a low density along one side of the container body 75 from one apex, and is gradually compressed to a high density as it approaches the other apex. It is stored in.
- the pressing force can be changed for each portion toward the center of the container body 75, and the entire outer peripheral surface can be pressurized in a balanced manner. By doing in this way, it becomes possible to press down in the direction which closes a crack part, and the shape of the container main body 75 can be maintained.
- FIG. 10 is a longitudinal sectional view of a sodium-sulfur battery 1 of Example 8 of the present invention
- FIG. 11 is a transverse sectional view thereof
- FIG. 12 is a partially enlarged view thereof.
- the sodium-sulfur battery 1 includes a container body 11 made of ⁇ -alumina having a circular cylindrical shape and a cathode chamber 18 inside, molten sulfur 13 held in the internal space of the container body 11, and the outer periphery of the container body 11.
- the compressed molten sodium 15, the metal communication pipe 16 communicating the sodium storage container 14 and the negative electrode member 12, and the outer peripheral surface of the container body 11 and the inner peripheral surface of the negative electrode member 12 are arranged in a compressed state.
- An urging member 17 made of a carbon fiber mat is used as a main component.
- the container main body 11 has a thick cylindrical shape, and the internal space corresponding to the shaft hole becomes the positive electrode chamber 18.
- the negative electrode member 12 is arranged along the outer peripheral surface of the container main body 11 with a slight gap, and is defined by the outer peripheral surface of the container main body 11 and the inner peripheral surface of the negative electrode member 12, and a slight space extending in a ring shape in the circumferential direction. Becomes the negative electrode chamber 19. A biasing member 17 is held in a compressed state in the negative electrode chamber 19.
- This container body 11 is manufactured by a known method of obtaining a rod-shaped molded body by ceramic extrusion molding, cutting it into a predetermined length, heating it to perform a degreasing process to remove a binder such as resin, and thereafter sintering. it can.
- the container body 11 can also be made by machining a block-shaped compact body obtained by compacting a powdered solid electrolyte into a predetermined shape and then sintering it.
- a first sealing ring 121 formed of ⁇ -alumina is bonded and fixed to the upper end surfaces of the container body 11 and the negative electrode member 12 with a glass adhesive or the like.
- the first sealing ring 121 functions to seal the upper end opening of the negative electrode chamber 19.
- the metal upper lid 123 is joined to the upper end surface of the first sealing ring 121 with a glass adhesive or the like, and the upper lid 123 and the negative electrode roll 12 are insulatively coupled via the first sealing ring 121.
- a second sealing ring 122 made of ⁇ -alumina is bonded and fixed to the lower end surfaces of the container body 11 and the negative electrode member 12 with a glass adhesive or the like.
- the second sealing ring 122 seals the lower end opening of the negative electrode chamber 19, and the negative electrode chamber 19 is formed as a sealed section.
- the metal bottom lid 124 is joined to the lower end surface of the second sealing ring 122 with a glass adhesive or the like, so that the positive electrode chamber 18 is formed as a sealed space. Further, the bottom lid 124 and the negative electrode member 12 are insulatively coupled via the second sealing ring 122.
- the part described above constitutes the positive electrode active material storage container of the present invention.
- a sodium storage container 14 separated from the positive electrode active material storage container is disposed on the upper cover 123 of the positive electrode active material storage container.
- the metal communication pipe 16 penetrates the lower end surface of the sodium storage container 14 and the side end surface of the negative electrode member 12 and is welded at the penetrated portion.
- Molten sodium 15 that is a negative electrode active material is held in the sodium container 14, and the molten sodium 15 flows into the negative electrode chamber 19 that extends in a ring shape through the communication pipe 16, and fills the entire negative electrode chamber 19 with the molten sodium 15. It will be. Further, between the outer peripheral surface of the container body 11 and the inner peripheral surface of the negative electrode member 12, as shown in FIG.
- the biasing member 17 made of a carbon fiber mat is compressed in the thickness direction, and the negative electrode It is stored in the member 12.
- a current collector 20 made of a carbon fiber aggregate impregnated with sulfur 13 as a positive electrode active material is inserted into the positive electrode chamber 18 formed in the container body 11. Further, a metal anode rod 23 is provided at the central portion of the current collector 20. The anode rod 23 is joined to the bottom lid 124. A cathode terminal 24 is joined to the sodium container 14. Furthermore, the anode terminal 25 is joined to the upper lid 123.
- the sodium-sulfur battery 1 of Example 8 has the above-described configuration. This sodium-sulfur battery 1 is used after being heated to a temperature of 290 ° C. to 350 ° C.
- molten sodium 15 in the negative electrode chamber 19 becomes sodium ions, passes through the solid electrolyte partition walls of the container body 11, moves to the positive electrode chamber 18, contacts and reacts with the molten sulfur 13, and discharges sodium sulfide. Generate.
- the same amount of molten sodium 15 moved from the negative electrode chamber 19 to the positive electrode chamber 18 by discharge is replenished from the molten sodium 15 stored in the sodium storage container 14. Therefore, at the time of discharge, the molten sodium 15 in the sodium container 14 decreases, and the sodium sulfide in the positive electrode chamber 18 increases.
- sodium sulfide in the positive electrode chamber 18 is decomposed to become sodium ions and molten sulfur 13, and the sodium ions permeate the portion of the container body 11 that becomes the partition wall of the solid electrolyte and move to the negative electrode chamber 19 to be molten sodium. 15 is generated and returned to the sodium container 14.
- a space inside the container body 11 is a positive electrode chamber 18, and a slight space between the outer peripheral surface of the container main body 11 and the inner peripheral surface of the negative electrode member 12 is a negative electrode chamber 19.
- the highly active molten sodium 15 can be stored only in a small amount in the small space, even if the container body 11 is damaged, a large amount of the molten sodium 15 does not leak out, and the safety is high. . Furthermore, most of the molten sodium 15 is held in a sodium storage container 14 that is provided separately from the positive electrode chamber 18, so that most of the molten sodium 15 and molten sulfur 13 can be kept away from each other. Increases nature. Furthermore, since the negative electrode chamber 19 is formed over almost the entire area of the outer peripheral surface of the container main body 11, a large area can be secured for the container main body 11 to function as a partition wall for the solid electrolyte, and the output of the battery is also large.
- the biasing member 17 is disposed in a compressed state between the outer peripheral surface of the container body 11 and the inner peripheral surface of the negative electrode member 12. Therefore, the biasing member 17 elastically pressurizes the container body 11 toward the center side by the repulsive force of the compression.
- the container body 11 Since the positive electrode chamber 18 is sealed under reduced pressure, the container body 11 is pressed from the outside of the container body 11 toward the axial direction and the axial direction due to a pressure difference with the atmosphere. Furthermore, the pressure in the positive electrode chamber 18 increases during discharge, and a force that presses the container main body 11 from the inside to the outside of the positive electrode chamber 18 works, and the container main body 11 can be pressed from both sides. Therefore, even if the container body 11 is broken and cracked, the pressing force presses it in the direction to close the cracked portion. Therefore, the shape of the container main body 11 before the crack is generated can be maintained, and leakage of the molten sodium 15 from the crack can be suppressed.
- FIG. 13 is a cross-sectional view in the case of using a container main body formed of a solid electrolyte and a second negative electrode roll 22 provided on the outer surface side thereof.
- FIG. 5 is a partially enlarged view thereof.
- the second negative electrode member 22 is disposed on the outer peripheral surface of the container body 11.
- the feature of the second negative electrode member 22 is that rectangular protrusions extending in the axial direction are provided at equal intervals on the inner surface.
- a method for providing the second negative electrode member 22 may be as follows. First, a circular second negative electrode member 22 as shown in FIG.
- the plate-like length in the longitudinal direction is formed slightly shorter than the outer circumference of the container body 11.
- the plate-shaped thing is wound around the container main body 11 along an outer peripheral surface direction. And it joins and closes in the state which pulled the both end surfaces of the plate-shaped thing wound along the outer peripheral surface direction.
- the container body 11 is pressed in the axial direction from the outside of the container body 11 in the axial direction and further in the axial direction from both end surfaces of the container body 11 due to a pressure difference with the atmosphere.
- the container body 11 is pressed in a direction in which the shape is reduced, that is, in a direction in which the circumference is reduced and the axial length is reduced. For this reason, even if the container main body 11 is damaged and a crack is generated, the pressing force presses the crack portion in the closing direction. Therefore, the shape of the container main body 11 before the crack is generated can be maintained, and leakage of the molten sodium 15 from the crack can be suppressed.
- FIG. 15 is a cross-sectional view in the case of using a container main body formed of a solid electrolyte and a second negative electrode member 32 provided on the outer surface side thereof.
- FIG. 16 is a partially enlarged view thereof.
- the third negative electrode member 32 is disposed on the outer peripheral surface of the container body 11. The feature of the third negative electrode member 32 is that the third negative electrode member 32 is bent and formed at equal intervals.
- the protrusions are alternately and continuously arranged on both the outer surface and the inner surface of the third negative electrode member 32.
- the same effect as that of the second negative electrode member 22 can be obtained.
- a plurality of pores formed between the projections on the inner surface of the third negative electrode member 32 form a part of the negative electrode chamber 39, and the molten sodium 15 is accommodated therein.
- the shape of the container body is not limited to the above, and for example, a container body 21 in which the shape of the container body 11 as shown in FIG. 17 is partially changed can be used. FIG.
- the container main body 21 is formed longer than the container main body 11 in the axial direction, and is provided with step portions on the upper end side peripheral surface and the lower end side peripheral surface thereof.
- the upper lid 123 and the bottom lid 124 are directly joined with a glass adhesive or the like at the upper end surface and the lower end surface of the container body 21.
- the negative electrode member 12, the top lid 123, and the bottom lid 124 can be joined with a glass adhesive or the like through a step portion provided on the side peripheral surface. This eliminates the need to provide a sealing ring, thus simplifying the configuration of the sodium-sulfur battery and reducing the cost.
- FIG. 18 is a longitudinal sectional view of the sodium sulfur battery 1 of Example 9 of the present invention
- FIG. 19 is a transverse sectional view thereof.
- the sodium-sulfur battery 1 includes a cylindrical positive electrode active material storage container 10 and a negative electrode active material storage container 30 that is separated and independent from the positive electrode active material storage container 10.
- the positive electrode active material storage container 10 has a circular cylindrical cylindrical body 11 made of ⁇ -alumina, a positive electrode chamber 18 formed in the inner space of the container main body 11, molten sulfur 16 held in the inner space, A cylindrical outer shell body 12 made of a metal plate disposed at an interval on the outer periphery of the container body 11, and a negative electrode chamber 19 formed in a ring-shaped gap between the outer shell body 12 and the container body 11.
- a soft sheet 24 made of aluminum foil that hermetically covers the outer peripheral surface of the main part is used as a main component.
- the container main body 11 has a thick cylindrical shape, and the internal space corresponding to the shaft hole becomes the positive electrode chamber 18.
- an anode rod 15 extending in the axial direction is disposed in the positive electrode chamber 18, and a lower end of the anode rod 15 is inserted through the bottom lid 23.
- the anode rod 15 has six plate-like spacing pieces 151 extending radially in the radial direction of the container body 11.
- the positive electrode chamber is formed into six compartments, and at the time of battery assembly, the positive electrode chamber 18 is configured by accommodating the conductive material 17 impregnated with sulfur 16 in each of the six compartments.
- the anode rod 15 has a hollow shape in the axial direction, and is used to adjust the pressure in the positive electrode chamber 18 during battery assembly.
- An outer shell 12 is disposed along the outer peripheral surface of the container main body 11 with a slight gap, and is partitioned by the outer peripheral surface of the container main body 11 and the inner peripheral surface of the outer shell 12 and extends in a ring shape in the circumferential direction.
- the negative electrode active material storage container 30 is disposed separately from the positive electrode active material storage container 10.
- the metal communication pipe 31 penetrates the lower end surface of the negative electrode active material storage container 30 and the side end surface of the outer shell body 12 and is welded at the penetrated portion.
- the negative electrode active material storage container 30 holds most of the molten sodium 14 that is the negative electrode active material.
- the molten sodium 14 passes through the communication pipe 31 and flows into the negative electrode chamber 19 that extends in a ring shape. Filled with molten sodium 14.
- a negative electrode terminal 25 is joined to the upper end surface of the negative electrode active material storage container 30.
- An upper lid 22 made of ⁇ -alumina is bonded and fixed to the upper end surface of the container body 11 by glass bonding, brazing, heat diffusion bonding, or the like.
- the upper lid 22 functions to seal the upper end opening of the positive electrode chamber 18.
- a bottom lid 23 made of ⁇ -alumina is bonded and fixed to the lower end surface of the container body 11 by glass bonding, brazing, heat diffusion bonding, or the like.
- the bottom lid 23 seals the lower end opening of the positive electrode chamber 18, and the positive electrode chamber 18 is formed as a sealed section.
- a fastening means for fastening the bottom lid 23 in the axial direction is provided on the lower end side of the anode rod 15, and the bottom lid 23 is more firmly sealed.
- the tightening means is provided with a spiral thread groove at the lower end of the anode rod 15, a washer 152 is disposed inside the bottom lid 23, and a metal nut 153 is screwed into the thread groove of the anode rod 15 from the outside of the bottom lid 23.
- the positive terminal 26 is joined to the tip of the metal nut 153.
- the cylindrical outer shell 12 disposed on the outer peripheral surface of the container main body 11 has narrow openings at the upper and lower ends. The narrowly formed portion is brought into contact with the outer peripheral surface of the container main body 11 and bonded and fixed by brazing, heat diffusion bonding, or the like, thereby forming the negative electrode chamber 19 as a sealed section.
- This positive electrode active material storage container 10 is further covered with a soft sheet 24 from the outside and hermetically sealed.
- the soft sheet 24 is made of an aluminum foil having a predetermined thickness.
- the means for hermetically sealing the positive electrode active material storage container 10 with the soft sheet 24 for example, the following can be considered. First, an aluminum foil is formed into a bag shape in advance, and the positive electrode active material storage container 10 is stored therein. Thereafter, a straw-like tube is inserted from the opening of the bag-like aluminum foil, and the internal gas (air) is removed by suction.
- the gas existing between the outer peripheral surface of the positive electrode active material storage container 10 and the inner peripheral surface of the soft sheet 24 made of aluminum foil is removed, and the inner peripheral surface of the soft sheet 24 becomes positive by the atmospheric pressure. It will be in the state pressed on the outer peripheral surface of the active material storage container 10. In this state, the positive electrode active material storage container 10 can be hermetically sealed with the soft sheet 24 by pulling out the straw-shaped tube from the opening of the bag-like aluminum foil and welding the openings together. At this time, as shown in FIG. 18, a cylindrical insulating member 121 is disposed between the outer shell body 12 and the soft sheet 24 to insulate the outer shell body 12 and the soft sheet 24.
- the metal nut 153, the positive electrode terminal 26, and the communication pipe 31 penetrate through the aluminum foil and are exposed to the outside of the flexible sheet 24.
- the insulating member 121 is arranged on the inner side in a portion where the communication pipe 31 penetrates the aluminum foil.
- the soft sheet 24 insulates and seals the end of the communication pipe 31 in an insulating manner.
- an insulating ring 154 is disposed outside the metal nut 153, and the soft sheet 24 insulates and seals the metal nut 153 in an insulating manner.
- the positive electrode active material storage container 10 of the sodium-sulfur battery 1 is structurally simple and airtightly sealed by the top lid 22 and the bottom lid 23. Furthermore, since it is hermetically housed in the soft sheet 24 from the outside, there is no risk of the molten sodium 14 or the molten sulfur 16 leaking out of the battery, and high safety can be ensured. Further, the pressure acting on the outer surface of the outer shell 12 acts as a force for compressing the circumferential direction of the container body 11 via the porous spacer 13 held in the negative electrode chamber 19.
- the sodium-sulfur battery 2 includes a cylindrical positive electrode active material storage container 20 and a negative electrode active material storage container 40 that is separated and independent from the positive electrode active material storage container 20.
- the positive electrode active material storage container 20 includes a container body 21 made of ⁇ -alumina in a circular cylindrical shape, a positive electrode chamber 28 formed in an internal space corresponding to the shaft hole of the container main body 21, and a melt held in the internal space.
- Sulfur 16 a fine negative electrode chamber 29 extending in the axial direction with a slight gap along the inner peripheral surface of the container main body 21 and formed in large numbers at a circumferential interval, and partly held in the fine pores.
- the soft sheet 34 is a main component.
- the container main body 21 has a thick cylindrical shape, and the internal space corresponding to the shaft hole becomes the positive electrode chamber 28.
- the anode rod 15 having the spacing piece 151 and extending in the axial direction is disposed in the positive electrode chamber 28, and the lower end of the anode rod 15 is inserted through the bottom lid 33.
- a conductive material 17 impregnated with sulfur 16 is accommodated in a section formed by the spacing pieces 151 and constitutes a positive electrode chamber 28.
- a large number of negative electrode chambers 29 are formed so as to surround the positive electrode chamber 28 along the inner wall surface of the container body 21 that partitions the positive electrode chamber 28.
- An upper lid 32 made of ⁇ -alumina is integrally bonded and fixed to the upper end surface of the container body 21 by glass bonding, brazing, heat diffusion bonding, or the like. The upper lid 32 functions to seal the upper end opening of the positive electrode chamber 28. Further, the upper lid 32 has a ring-shaped groove on its lower surface, and the opening surface of the groove is closed by the upper end surface of the container body 21 to form a ring-shaped passage 321.
- the ring-shaped passage 321 communicates with the upper end openings of all the negative electrode chambers 29 of the container body 21. Further, the upper cover 32 has a lead-out port 323 extending to the ring-shaped passage 321 and having the inside as a vertical passage 322. The outlet port 323 is joined and fixed to the communication pipe 41 connected to the negative electrode active material storage container 40.
- a bottom lid 33 made of ⁇ -alumina is integrally bonded and fixed to the lower end surface of the container body 21 by glass bonding, brazing, heat diffusion bonding, or the like.
- the bottom lid 33 seals the lower end opening of the negative electrode chamber 29 and the lower end opening of the positive electrode chamber 28 provided at equal intervals in the circumferential direction of the container body 21, and the negative electrode chamber 29 and the positive electrode chamber 28 form a sealed section. Further, a fastening means for fastening the bottom cover 33 in the axial direction is provided on the lower end side of the anode rod 15, and the bottom cover 33 is further firmly sealed.
- the tightening means is provided with a spiral groove at the lower end of the anode rod 15, a washer 152 is arranged inside the bottom lid 33, and a metal nut 153 is screwed into the thread groove of the anode rod 15 from the outside of the bottom lid 33. The bottom lid 33 is tightened in the axial direction.
- the positive terminal 26 is joined to the tip of the metal nut 153.
- the negative electrode active material storage container 40 is disposed separately from the positive electrode active material storage container 20.
- the metal communication pipe 41 penetrates the lower end surface of the negative electrode active material storage container 40, and the other end is welded and fixed to the outlet port 323.
- the negative electrode active material storage container 40 holds most of the molten sodium 14 that is the negative electrode active material.
- the molten sodium 14 passes through the communication pipe 41, the vertical passage 322, the ring-shaped passage 321, and all the negative electrode chambers 29.
- the negative electrode chamber 29 is filled.
- the negative electrode terminal 25 is joined to the upper end surface of the negative electrode active material storage container 40.
- the positive electrode active material storage container 20 is covered with a soft sheet 34 from the outside and hermetically sealed.
- the soft sheet 34 is made of an aluminum foil having a predetermined thickness.
- the airtight sealing means by the soft sheet 34 is the same as that described in the first embodiment.
- the metal nut 153, the positive electrode terminal 26, and the outlet port 323 pass through the aluminum foil and are exposed to the outside of the flexible sheet 34.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
Description
これに対応して種々の改良がなされている(特開平3-187160号、特開平6-196204号)。
縦断面図である。
本発明の負極活物質収納容器は、負極室に保持されている以外の残りの負極活物質を収納するもので、負極活物質の大部分をこの負極活物質収納容器に収納することで、大部分の負極活物質と正極活物質を互いに遠ざけることができ、安全性が増す。また、放電時には、放電反応により減少した負極活物質の分だけ、負極活物質収納容器から負極室に負極活物質を供給することができるため、負極室に収納することのできる負極活物質の量が少なくても、電池容量を低下させることはない。
負極活物質収納容器は、負極活物質に耐食性のある材料、好ましくは耐食性のある金属材料で形成されている。負極活物質収納容器の形状は容器として機能するものであれば特定のものに限られない。
本発明の正極活物質収納容器は、少なくとも一個の正極室と、この正極室を区画する壁面に沿いこの壁面より間隔を隔て区画された複数個の負極室と、をもつものとすることができる。より具体的に、正極室及び負極室は、共に軸方向に並んで延びる孔状(シリンダ状)とすることができる。この正極活物質収納容器の外形を柱形状とすることができる。
この付勢部材は、例えば、耐熱性を有する炭素繊維、ガラス繊維などを圧縮したり薄いマット状にしたものとすることができる。この付勢部材を正極活物質収納容器の少なくとも一部の外側面に当接することで、その収納容器をその中心側に向かって弾性的に加圧する。そのため、万一、正極活物質収納容器が破損して亀裂が生じたとしても、その加圧の力が亀裂部分を閉じる方向に押さえ込む。従って、亀裂が生じる前の容器形状体を維持することができ、亀裂から正極活物質が漏れ出すことを抑制できる。したがって、付勢部材を設けることで、正極活物質収納容器の亀裂の発生が抑えられ、負極活物質と正極活物質の混合を防止することができる。
正極活物質の収容空間とし一軸方向に延びる形状のものをいう。容器本体の外周形状は、円形、楕円形、三角形、四角形等任意の形状とすることができる。本発明の固体電解質二次電池では、容器本体の内側面で区画形成される空間を正極室とするため、その正極室は軸方向に延びるものであって、その断面形状は、円形、楕円形、三角形、四角形等任意の形状とすることもできる。
このナトリウム硫黄電池1は、金属製の筒状の保護缶11と、この保護缶11の空間内の上部に、ガラス繊維マットで形成される絶縁体12を介して保持されたナトリウム容器13と、ナトリウム容器13内に保持された溶融ナトリウム14と、保護缶11の空間内の下部に保持された筒状でβアルミナで作られる筒状の容器本体15と、この内部空間に保持される溶融硫黄16と、容器本体15の外周面と保護缶11の内周面との間に圧縮状態で配置されている炭素繊維のマットからなる付勢部材17を主な構成部分としている。
容器本体15は図3に示すように、肉厚の筒状で、軸孔に当たる内部空間が正極室18となる。この容器本体15の内周面に沿い僅かの間隙を隔てて軸方向に延びる細孔状の負極室19が周方向に間隔を隔て多数形成されている。この容器本体15は、セラミック押し出し成形で棒状の成形体を得、これを所定長さに切断し、加熱して樹脂等の結合剤を除く脱脂行程を行い、その後焼結する公知の方法で製造できる。なお、容器本体15は、粉末状の固体電解質を圧蜜化したブロック状の圧蜜体を機械加工して所定の形状とし、その後焼結して作ることもできる。
この容器本体15の上端面には、αアルミナで形成される上蓋151がガラス接着材等で一体的に接合固定される。この上蓋151は、その下面にリング状の溝を持ち、この溝の開口面が容器本体15の上端面で閉じられてリング状通路152となる。このリング状通路152には、容器本体15の全ての負極室19の上端開口と連通する。この上蓋151の上面からリング状通路152に延びる垂直通路153をもつ。
容器本体15の下端面には、αアルミナで形成された封止リング155がガラス接着材等で一体的に接合固定される。この封止リング155は容器本体15の周方向に等間隔で設けられた負極室19の下端開口を封止する働きをする。
上蓋151の上にナトリウム収納容器13が配置される。ナトリウム収納容器13の底には貫通孔が形成されており、この貫通孔とこの貫通孔と共穴となる垂直通路153とに、軸孔を持つ金属製の接続管154が挿着接合される。
ナトリウム収納容器13には溶融ナトリウム14が保持され、溶融ナトリウム14は、接続管154の軸孔、垂直通路153、リング状通路152を通り、全ての負極室19に流入し、負極室19を満たすことになる。
また、容器本体15の外周面と保護缶11の内周面との間には、図1に示すように、炭素繊維マットからなる付勢部材17が厚さ方向に圧縮された状態で、保護缶11に納められる。容器本体15に形成された正極室18には正極活物質である硫黄16が含浸された炭素繊維集積体からなる集電体20が挿着される。さらにこの集電体20中心部分に金属製の陽極棒21が設けられる。
正極室18の底には、金属製の底蓋111が容器本体15の下端面にガラス接着材で接合され、正極室18が閉空間として形成される。
なお、底蓋111は保護缶11の側周部に溶接され保護缶11の底部となる。この底蓋111には陽極棒21が接合される。また、ナトリウム収納容器13には陰極端子22が接合され、その上側部分は保護缶11の通し穴を通って上方に突出している。さらに保護缶11の上側には陽極端子23が接合されている。
実施例1のナトリウム硫黄電池1は上述した構成からなる。
このナトリウム硫黄電池1は300℃~350℃の温度に加熱されて使用される。放電時に負極室18内の溶融ナトリウム14がナトリウムイオンとなり容器本体15の固体電解質の隔壁となる部分を透過して正極室18に移動し、溶融硫黄16と接触反応して放電し、硫化ナトリウムを生成する。放電により負極室19から正極室18に移動した同じ量の溶融ナトリウム14はナトリウム収納容器13に収納されている溶融ナトリウム14から補充される。従って、放電時にはナトリウム収納容器13内の溶融ナトリウム14が減り、正極室18内の硫化ナトリウムが増加することになる。
充電時には、正極室18内の硫化ナトリウムが分解してナトリウムイオンと溶融硫黄16になり、ナトリウムイオンが容器本体15の固体電解質の隔壁となる部分を透過して負極室19に移動して溶融ナトリウム14を生成し、ナトリウム収納容器13内に戻る。
このナトリウム硫黄電池1では、容器本体15の内部に正極室18と負極室19をもつため、従来のナトリウム硫黄電池に比べて構造が非常に単純であり、電池を構成する部品も少なくすることができる。また、負極室19は細孔状に形成され、1室あたりの容積が小さいため、収納される溶融ナトリウム14の量を減少させることができる。そして大部分の溶融ナトリウム14は、正極室18と離隔して設けられたナトリウム収納容器13内に保持されているため、大部分の溶融ナトリウム14と溶融硫黄16を互いに遠ざけることができ、安全性が増す。
さらに、溶融ナトリウム14は複数の負極室19に分割して収納されているため、万一容器本体15が破損しても、溶融硫黄16と直接反応する溶融ナトリウム14の量を抑えることができる。
また、負極室19内に収納される溶融ナトリウム14の量は少量であるが、上述したように、ナトリウム収納容器13から溶融ナトリウム14が補充されるため、負極室19には常に一定量の溶融ナトリウム14を収納することができる。そのため、溶融ナトリウム14が不足して電池容量が低下するという問題は生じない。
また、付勢部材17は、容器本体15の外周面と保護缶11の内周面との間に圧縮状態で配置されている。そのため、その圧縮の反撥力により付勢部材17は、容器本体15をその中心側に向かって弾性的に加圧している。そのため、万一、容器本体15が破損して亀裂が生じたとしても、その加圧の力が亀裂部分を閉じる方向に押さえ込む。従って、亀裂が生じる前の容器本体15の形状を維持することができ、亀裂から溶融ナトリウム14が漏れ出すことを抑制できる。
なお、容器本体15の形状は実施例1で示したものに限られず、様々な形状が考えられる。実施例1とは異なった形状の容器本体を有するナトリウム硫黄電池の横断面図を図4~図9に示した。以下、図4~図9に基づいてそれぞれ異なった形状の容器本体について説明する。なお、図4~図9では、溶融硫黄、集電体及び陽極棒は省略して図示してある。
実施例2のナトリウム硫黄電池の容器本体25は、実施例1の図2に示す容器本体15と同様に、外周形状が円形の軸方向に延びる柱形状である。この容器本体25は、金属製の筒状の保護缶11に収納され、容器本体25の外周面と保護缶11の内周面との間に付勢部材17が配置される。容器本体25の内部には、図4に示すように、3つの相対する正極室28が形成されている。各正極室28は、断面円形状の軸方向に延びる孔状である。そして、3つの正極室28の壁面に沿いかつこの壁面より僅かな間隙を隔てて負極室29が周方向に等間隔で多数形成されている。負極室29は、軸方向に延びる細孔状である。
容器本体25をこのような形状とすることで、正極室28に収納される溶融硫黄の量は減ることになる。従って、単セルあたりの電池容量は減少することになる。しかし、正極室28の数が増えているため、正極室28と負極室29とが間隙を隔てて接する面積はより広くなる。すなわち固体電解質の隔壁となる面積を広くとることができ、より多くのナトリウムイオンが電解質を透過して反応することができるのである。また、一部の負極室29は隣接する正極室28の兼用となっているため、さらに多くのナトリウムイオンが電解質を透過して反応することができる。したがって、容器本体25をこのような形状とすることで、単セルあたりの電池の出力を上昇させることができる。
この容器本体35は、外周形状が円形の軸方向に延びる柱形状である。
容器本体35は、金属製の筒状の保護缶11に収納され、容器本体35の外周面と保護缶11の内周面との間に付勢部材17が配置される。容器本体35の内部には7つの正極室38が形成されている。各正極室38は、断面円形状の軸方向に延びる孔状である。そして、7つの正極室38の壁面に沿いかつこの壁面より僅かな間隙を隔てて負極室39が周方向に等間隔で多数形成されている。負極室39は、軸方向に延びる細孔状である。
容器本体35をこのような形状とすることで、1個当たりの正極室38に収納される溶融硫黄の量はさらに減ることになる。しかし、正極室38の数がさらに増えているため、固体電解質の隔壁となる面積を広くとることができる。また、隣接する正極室38の兼用となる負極室29の数も増えているため、さらに多くのナトリウムイオンが固体電解質を透過して反応することができる。したがって、容器本体35をこのような形状とすることで、単セルあたりの電池の出力をより上昇させることができる。
容器本体45をこのような形状とすることで、単セルあたりの電池容量は減少するものの、実施例2、実施例3で述べたのと同様の理由により、さらに電池の出力を上昇させることができる。
容器本体55をこのような形状とすることで、内部に形成できる負極室59の数は少なくなる。しかし、負極室59を半円形状の凸部の壁面で囲うことにより固体電解質の隔壁となる面積を広くとることができる。したがって、単セルあたりの電池の出力を上昇させることができる。また、負極室59の数が少なくなった分だけ正極室58の容積を広くとることができるため、より多くの溶融硫黄を収納することができる。従って、単セルあたりの電池容量を増やすことができる。
容器本体65をこのような形状とすることで、一定の空間に有効に正極室68及び負極室69を形成することができる。また、隣り合う二つの正極室68の内側の壁面に沿って形成される負極室69は、その二つの正極室68の兼用となっているため、多くのナトリウムイオンが電解質を透過して反応することができる。
さらに、炭素繊維のマットからなる付勢部材67が、断面四角形状の容器本体65の4つの頂点部分で高密度に圧縮された状態で収納されている。また、付勢部材67は、一方の頂点から、容器本体65の一辺に沿って、徐々に低密度に圧縮された状態で収納され、他方の頂点に近づくにつれ徐々に高密度に圧縮された状態で収納されている。このように付勢部材67を配置することで、4つの頂点方向から容器本体65の中心に向かって、他の外周面に比べてより強く弾性的に加圧することが可能となる。多角形状の頂点部分は、他の部分に比べて外的圧力に強い性質を持つため、部分ごとにおいて加圧力を変えることで、外周面全体をバランスよく加圧することできる。このようにすることで、亀裂部分を閉じる方向に押さえ込むことが可能となり、容器本体65の形状を維持することができる。
容器本体75をこのような形状とすることで、一定の空間に効率良く正極室78及び負極室79を形成することができる。また、隣り合う二つの正極室79の兼用となる負極室79が多数形成されているため、より多くのナトリウムイオンが電解質を透過して反応することができる。
さらに、炭素繊維のマットからなる付勢部材77が、断面六角形状の容器本体75の6つの頂点部分で高密度に圧縮された状態で収納されている。また、付勢部材77は、一方の頂点から、容器本体75の一辺に沿って、徐々に低密度に圧縮された状態で収納され、他方の頂点に近づくにつれ徐々に高密度に圧縮された状態で収納されている。
このように付勢部材77を配置することで、容器本体75の中心に向かって、部分ごとにおいて加圧力を変えることができ、外周面全体をバランスよく加圧することできる。このようにすることで、亀裂部分を閉じる方向に押さえ込むことが可能となり、容器本体75の形状を維持することができる。
このナトリウム硫黄電池1は、円形の筒状で内部が正極室18となるβアルミナで作られる容器本体11と、この容器本体11の内部空間に保持される溶融硫黄13と、容器本体11の外周面に配され容器本体11とともに負極室19を区画する金属板製の筒状の負極部材12と、負極部材12と分離独立して設けられたナトリウム収納容器14と、ナトリウム収納容器14内に保持された溶融ナトリウム15と、ナトリウム収納容器14と負極部材12とを連通する金属製の連通管16と、容器本体11の外周面と負極部材12の内周面との間に圧縮状態で配置されている炭素繊維のマットからなる付勢部材17を主な構成部分としている。
容器本体11は図11に示すように、肉厚の筒状で、軸孔に当たる内部空間が正極室18となる。この容器本体11の外周面に沿い僅かの間隙を隔てて負極部材12が配置され、容器本体11の外周面と負極部材12の内周面とによって区画され周方向にリング状に延びる僅かな空間が負極室19となる。負極室19内には、付勢部材17が圧縮状態で保持されている。この容器本体11は、セラミック押し出し成形で棒状の成形体を得、これを所定長さに切断し、加熱して樹脂等の結合剤を除く脱脂行程を行い、その後焼結する公知の方法で製造できる。なお、容器本体11は、粉末状の固体電解質を圧蜜化したブロック状の圧蜜体を機械加工して所定の形状とし、その後焼結して作ることもできる。
容器本体11と負極部材12との上端面には、αアルミナで形成される第1の封止リング121がガラス接着材等で接合固定される。第1の封止リング121は、負極室19の上端開口を封止する働きをする。金属製の上蓋123は、第1の封止リング121の上端面にガラス接着材等で接合され、上蓋123と負極ロール12は第1の封止リング121を介して絶縁的に結合される。
容器本体11と負極部材12との下端面には、αアルミナで形成された第2の封止リング122がガラス接着材等で接合固定される。第2の封止リング122は、負極室19の下端開口を封止し、負極室19が密閉区間として形成される。金属製の底蓋124は第2の封止リング122の下端面にガラス接着材等で接合され、正極室18が密閉空間として形成される。また、底蓋124と負極部材12は第2の封止リング122を介して絶縁的に結合されている。
以上説明した部分が本発明の正極活物質収納容器を構成する。
この正極活物質収納容器の上蓋123の上部には、正極活物質収納容器と別体として分離したナトリウム収納容器14が配置される。金属製の連通管16は、ナトリウム収納容器14の下端面と負極部材12の側端面をそれぞれ貫通し、その貫通した部分で溶接されている。
ナトリウム収納容器14には負極活物質である溶融ナトリウム15が保持され、溶融ナトリウム15は、連通管16を通り、リング状に延びる負極室19に流入し、負極室19全体を溶融ナトリウム15で満たすことになる。
また、容器本体11の外周面と負極部材12の内周面との間には、図10に示すように、炭素繊維マットからなる付勢部材17が厚さ方向に圧縮された状態で、負極部材12に納められる。容器本体11に形成された正極室18には正極活物質である硫黄13が含浸された炭素繊維集積体からなる集電体20が挿着される。さらにこの集電体20中心部分に金属製の陽極棒23が設けられる。
この底蓋124には陽極棒23が接合される。また、ナトリウム収納容器14には陰極端子24が接合される。さらに上蓋123には陽極端子25が接合されている。
実施例8のナトリウム硫黄電池1は上述した構成からなる。
このナトリウム硫黄電池1は290℃~350℃の温度に加熱されて使用される。放電時に負極室19内の溶融ナトリウム15がナトリウムイオンとなり容器本体11の固体電解質の隔壁となる部分を透過して正極室18に移動し、溶融硫黄13と接触反応して放電し、硫化ナトリウムを生成する。放電により負極室19から正極室18に移動した同じ量の溶融ナトリウム15はナトリウム収納容器14に収納されている溶融ナトリウム15から補充される。従って、放電時にはナトリウム収納容器14内の溶融ナトリウム15が減り、正極室18内の硫化ナトリウムが増加することになる。
充電時には、正極室18内の硫化ナトリウムが分解してナトリウムイオンと溶融硫黄13になり、ナトリウムイオンが容器本体11の固体電解質の隔壁となる部分を透過して負極室19に移動して溶融ナトリウム15を生成し、ナトリウム収納容器14内に戻る。
このナトリウム硫黄電池1では、容器本体11の内側の空間を正極室18とし、この容器本体11の外周面と負極部材12の内周面との間の僅かな空間を負極室19としている。このため、活性の高い溶融ナトリウム15はその僅かな空間に少量しか収納することができないため、万一容器本体11が破損したとしても多量に溶融ナトリウム15が漏れ出すことがなく、安全性が高い。さらに、大部分の溶融ナトリウム15は、正極室18と離隔して設けられたナトリウム収納容器14内に保持されているため、大部分の溶融ナトリウム15と溶融硫黄13を互いに遠ざけることができ、安全性が増す。
さらに、容器本体11の外周面のほぼ全領域にわたって負極室19を形成しているため、容器本体11が固体電解質の隔壁として機能する面積を大きく確保することができ電池の出力も大きい。
また、負極室19内に収納される溶融ナトリウム15の量は少量であるが、上述したように、ナトリウム収納容器14から溶融ナトリウム15が補充されるため、負極室19には常に一定量の溶融ナトリウム15を収納することができる。そのため、溶融ナトリウム15が不足して電池容量が低下するという問題は生じない。
また、付勢部材17は、容器本体11の外周面と負極部材12の内周面との間に圧縮状態で配置されている。そのため、その圧縮の反撥力により付勢部材17は、容器本体11をその中心側に向かって弾性的に加圧している。また正極室18は減圧下において封止されているため、容器本体11は大気との圧力差により容器本体11の外側から軸心方向及び軸方向に向かって押圧される。さらに、放電時には正極室18内の圧力が高くなり、正極室18の内側から外側に向かって容器本体11を押圧する力が働き、容器本体11を両面から押圧することが可能となる。そのため、万一、容器本体11が破損して亀裂が生じたとしてもその押圧の力が亀裂部分を閉じる方向に押さえ込む。従って、亀裂が生じる前の容器本体11の形状を維持することができ、亀裂から溶融ナトリウム15が漏れ出すことを抑制できる。
なお、負極部材12の形状は上記したものに限られるものではなく、例えば、図13に示すような第2負極部材22を用いることもできる。
図13は、固体電解質で形成された容器本体とその外側面側に設けられた第2負極ロール22を用いた場合の横断面図である。また、図5はその部分的拡大図である。図13に示すように、容器本体11の外周面に第2負極部材22が配置されている。この第2負極部材22の特徴は、内側面に軸方向に延びる矩形状の突起を等間隔で有していることである。この第2負極部材22を設ける方法としては以下のものによるとよい。まず、図13で示すような円形の第2負極部材22を一旦開いて直線の板状にしたものをあらかじめ形成しておく。その板状の長手方向の長さは、容器本体11の外周の長さよりも少し短めに形成しておく。そして外周面方向に沿ってその板状のものを容器本体11に巻きつける。そして、外周面方向に沿って巻きつけた板状のものの両端面を引っ張った状態で接合して閉じる。
これによって、第2負極部材22の内側面に形成された複数の矩形状の突起の先端が容器本体11の外周面を当接し、その突起の先端が容器本体11の外周面をその中心側、すなわち軸心に向かって押圧する。また正極室18は減圧下において封止されているため、容器本体11は大気との圧力差により容器本体11の外側から軸心方向にさらには容器本体11の両端面側から軸方向に押圧される。この結果、容器本体11はその形状が小さくなる方向に、すなわち円周が小さくなり軸方向の長さが短くなる方向に押圧される。このため、万一、容器本体11が破損して亀裂が生じたとしても、その押圧の力が亀裂部分を閉じる方向に押さえ込む。従って、亀裂が生じる前の容器本体11の形状を維持することができ、亀裂から溶融ナトリウム15が漏れ出すことを抑制できる。なお、この場合、第2負極部材22の内側面に複数形成される突起と突起との間の矩形状の空間が負極室29の一部を形成し、そこに溶融ナトリウム15が収納されることになる。
さらに、図15に示すような第3負極部材32を用いることもできる。なお、図15は、固体電解質で形成された容器本体とその外側面側に設けられた第2負極部材32を用いた場合の横断面図である。また、図16はその部分的拡大図である。図15に示すように、容器本体11の外周面に第3負極部材32が配置されている。この第3負極部材32の特徴は、等間隔に波状に屈曲形成されていることである。これにより、第3負極部材32の外側面と内側面の両面に突起が交互に連続して並ぶ形状となっている。
これを上述の場合と同様の方法により設けた場合、第2負極部材22の場合と同様の効果を得ることができる。
なお、この場合、第3負極部材32の内側面に複数形成される突起と突起との間の細孔状の空間が負極室39の一部を形成し、そこに溶融ナトリウム15が収納されることになる。また、容器本体の形状は上記したものに限られるものではなく、例えば、図17に示すような容器本体11の形状に部分的な変更を加えた容器本体21を用いることもできる。
図17は、固体電解質で形成された容器本体21を用いた場合のナトリウム硫黄電池2の縦断面図である。
容器本体21は、容器本体11よりも軸方向の長さを長く形成し、その上端側周面と下端側周面にそれぞれ段差部を設けたものである。容器本体21の上端面と下端面では直接に上蓋123と底蓋124とをガラス接着材等で接合する。また側周面に設けた段差部を介して負極部材12と上蓋123及び底蓋124とをガラス接着材等で結合することができる。
これによって、封止リングを設ける必要がなくなるから、ナトリウム硫黄電池の構成を単純化してコストを低くすることが可能である。
容器本体11は図19に示すように、肉厚の筒状で、軸孔に当たる内部空間が正極室18となる。さらに正極室18内には、軸方向に延びる陽極棒15が配置され、その下端が底蓋23を貫通挿入している。この陽極棒15は、容器本体11の径方向に放射状に延びる6枚の板状の間隔片151を有している。これにより正極室は6個の区画に形成され、電池組立時には、この6個の区画にそれぞれ、硫黄16を含浸した導電材17を収納して正極室18が構成される。また、図19に示すように、陽極棒15は、軸方向に中空の形状となっており、電池組立時には、正極室18内の圧力を調節するのに用いられる。
また、容器本体11の外周面に沿い僅かの間隙を隔てて外殻体12が配置され、容器本体11の外周面と外殻体12の内周面とによって区画され周方向にリング状に延びる僅かな空間が負極室19となる。負極室19内には、金属繊維を圧縮した多孔質スペーサー13が保持されている。
負極活物質収納容器30は正極活物質収納容器10とは分離独立して配置されている。そして、金属製の連通管31が、負極活物質収納容器30の下端面と外殻体12の側端面をそれぞれ貫通し、その貫通した部分で溶接されている。負極活物質収納容器30には負極活物質である溶融ナトリウム14の大部分が保持され、溶融ナトリウム14は、連通管31を通り、リング状に延びる負極室19に流入し、負極室19全体を溶融ナトリウム14で満たしている。また、負極活物質収納容器30の上端面には負極端子25が接合されている。
容器本体11の上端面は、αアルミナで作られる上蓋22がガラス接合、ろう付又は熱拡散接合等で接合固定される。この上蓋22は、正極室18の上端開口を封止する働きをする。容器本体11の下端面は、αアルミナで作られる底蓋23がガラス接合、ろう付又は熱拡散接合等で接合固定される。底蓋23は、正極室18の下端開口を封止し、正極室18が密閉区間として形成される。
さらに、陽極棒15の下端側には、底蓋23を軸方向に締め付ける締付手段が備えられており、底蓋23はさらに強固に封止される。締付手段は、陽極棒15の下端に螺旋状のねじ溝を設け、底蓋23の内側に座金152を配し、底蓋23の外側から陽極棒15のねじ溝に金属ナット153を螺合して底蓋23を軸方向に締め付けるものである。なお、金属ナット153の先端には正極端子26が接合されている。
また、容器本体11の外周面に配される円筒状の外殻体12は、図18に示すように、上端及び下端において開口部を狭く形成している。その狭く形成した部分を容器本体11の外周面に当接させ、ろう付又は熱拡散接合等で接合固定することで、負極室19を密閉区間として形成する。
この正極活物質収納容器10は、さらに外側から軟質シート24によって覆われ、気密封止されている。軟質シート24は、所定の厚さを有するアルミニウム箔からなる。この場合、正極活物質収納容器10を軟質シート24によって気密封止する手段としては、例えば、次のものが考えられる。まず、あらかじめアルミニウム箔を袋状に成形しておいて、正極活物質収納容器10をその内部に収納する。その後、袋状のアルミニウム箔の開口部からストロー状の管を差し込み、内部の気体(空気)を吸引除去する。このとき、正極活物質収納容器10の外周面とアルミニウム箔からなる軟質シート24の内周面との間に存在していた気体は除去され、大気圧により、軟質シート24の内周面は正極活物質収納容器10の外周面に押着された状態となる。そしてこの状態のまま、袋状のアルミニウム箔の開口部からストロー状の管を抜いて、開口部を相互溶接することにより正極活物質収納容器10を軟質シート24によって気密封止することができる。
この際、図18に示すように、外殻体12と軟質シート24との間には、円筒状の絶縁部材121が配置され、外殻体12と軟質シート24とを絶縁している。また、金属ナット153、正極端子26及び連通管31は、アルミニウム箔を貫通して、軟質シート24の外部に露出される。さらに、連通管31は外殻体12と電気的に接続されているため、図18で示すように、連通管31がアルミニウム箔を貫通する部分において内側に絶縁部材121が配置されるようにして、軟質シート24が連通管31の端部を絶縁的に接着封止している。
さらに、図18に示すように、金属ナット153の外側には絶縁リング154を配置して、軟質シート24が金属ナット153を絶縁的に接着封止している。
以上のようにナトリウム硫黄電池1の正極活物質収納容器10は、上蓋22及び底蓋23により構造的に単純でかつ気密的に封止されている。さらに、外側から軟質シート24に密閉収納されているため、溶融ナトリウム14や溶融硫黄16が電池の外部に漏れ出すおそれがなく、高い安全性を確保することができる。
また、外殻体12の外側面に作用する圧力が、負極室19内に保持される多孔質スペーサー13を介して、容器本体11の周方向を圧縮する力として作用する。これにより、万一容器本体11が破損して亀裂が生じたとしても、その圧縮する力が亀裂部分を閉じる方向に押さえ込むため、容器本体11の形状を維持することができ、亀裂から活物質が漏れ出すことを抑制できる。
このナトリウム硫黄電池2は、円筒形状の正極活物質収納容器20と、正極活物質収納容器20と分離独立する負極活物質収納容器40とから構成されている。正極活物質収納容器20は、円形の筒状でβアルミナから作られる容器本体21と、この容器本体21の軸孔に当たる内部空間に形成される正極室28と、この内部空間に保持される溶融硫黄16と、容器本体21の内周面に沿い僅かの間隙を隔てて軸方向に延び周方向に間隔を隔て多数形成される細孔状の負極室29と、この細孔に一部保持される溶融ナトリウム14と、容器本体21の上端部及び下端部を封止するαアルミナで作られる上蓋32及び底蓋33と、正極活物質収納容器20の外周面を気密的に覆うアルミニウム箔製の軟質シート34を主な構成部分としている。
容器本体21は肉厚の筒状で、軸孔に当たる内部空間が正極室28となる。また、実施例9で説明したのと同様に、正極室28内には、間隔片151を有し軸方向に延びる陽極棒15が配置され、その下端が底蓋33を貫通挿入している。また、間隔片151によって形成される区画には、硫黄16を含浸した導電材17が収納され正極室28を構成する。
負極室29は、正極室28を区画する容器本体21の内壁面に沿って、正極室28を囲むように多数形成されている。
容器本体21の上端面には、αアルミナで作られる上蓋32がガラス接合、ろう付又は熱拡散接合等で一体的に接合固定される。この上蓋32は、正極室28の上端開口を封止する働きをする。さらに、この上蓋32は、その下面にリング状の溝を持ち、この溝の開口面が容器本体21の上端面で閉じられてリング状通路321となる。このリング状通路321には、容器本体21の全ての負極室29の上端開口と連通する。さらにこの上蓋32の上面にはリング状通路321に延び内部を垂直通路322とする導出口323をもつ。導出口323は、負極活物質収納容器40に繋がる連通管41と接合固定される。
容器本体21の下端面には、αアルミナで作られた底蓋33がガラス接合、ろう付又は熱拡散接合等で一体的に接合固定される。この底蓋33は容器本体21の周方向に等間隔で設けられた負極室29の下端開口と正極室28の下端開口を封止し、負極室29及び正極室28が密閉区間として形成する。
さらに、陽極棒15の下端側には、底蓋33を軸方向に締め付ける締付手段が備えられており、底蓋33はさらに強固に封止される。締付手段は、陽極棒15の下端に螺旋状の溝を設け、底蓋33の内側に座金152を配し、底蓋33の外側から陽極棒15のねじ溝に金属ナット153を螺合して底蓋33を軸方向に締め付けるものである。なお、金属ナット153の先端には正極端子26が接合されている。
負極活物質収納容器40は正極活物質収納容器20とは分離独立して配置されている。そして、金属製の連通管41が、負極活物質収納容器40の下端面を貫通し、さらにもう一端が導出口323と溶接固定されている。負極活物質収納容器40には負極活物質である溶融ナトリウム14の大部分が保持され、溶融ナトリウム14は、連通管41を通り、垂直通路322、リング状通路321を通り、全ての負極室29に流入し、負極室29を満たすことになる。また、負極活物質収納容器40の上端面には負極端子25が接合されている。
さらに、正極活物質収納容器20は、外側から軟質シート34によって覆われ、気密封止されている。軟質シート34は、所定の厚さを有するアルミニウム箔からなる。この軟質シート34による気密封止手段は、実施例1で述べたのと同様である。このとき、金属ナット153、正極端子26及び導出口323は、アルミニウム箔を貫通して、軟質シート34の外部に露出されている。
Claims (16)
- 負極活物質と、
正極活物質と、
該負極活物質の一部を収納する負極活物質収納容器と、
該正極活物質を保持する正極室の少なくとも一部と該負極活物質の他の一部を保持する負極室の少なくとも一部とを区画すると共に該負極活物質を通す固体電解質で、該負極活物質収納容器と別体として形成された正極活物質収納容器と、
を有することを特徴とする固体電解質二次電池。 - 前記正極活物質収納容器は、少なくとも一個の前記正極室と、前記正極室を区画する壁面に沿い前記壁面より間隔を隔て区画された複数個の前記負極室と、をもつ請求項1記載の固体電解質二次電池。
- 前記正極室及び前記負極室は、共に軸方向に並んで延びる孔状である請求項2記載の固体電解質二次電池。
- 前記正極活物質収納容器は、柱形状である請求項3記載の固体電解質二次電池。
- 前記正極活物質収納容器の少なくとも一部の外側面に当接し、前記正極活物質収納容器を中心側に付勢する付勢部材をもつ請求項1記載の固体電解質二次電池。
- 前記正極活物質収納容器は、内部に前記正極室を区画する前記固体電解質で形成された筒状の容器本体と前記容器本体の外周面を覆い該外周面との間に前記負極室を形成する負極部材とからなる請求項1記載の固体電解質二次電池。
- 前記負極部材は、内面側に軸方向に延び先端が前記筒状壁の外周面を押圧する突条を所定の間隔で有する請求項6記載の固体電解質二次電池。
- 前記負極部材は、前記筒状壁の外周面に沿って延びる波状部分をもつ請求項6記載の固体電解質二次電池。
- 前記負極室は、多孔質のスペーサをもつ請求項6記載の固体電解質二次電池。
- 前記正極活物質収納容器は、前記固体電解質で形成された筒状壁とその上側及び下側にそれぞれ固定されたセラミック製の上蓋及び底蓋を有し、
さらに、前記正極活物質収納容器の外周面を気密的に覆う軟質シートを有する請求項1記載の固体電解質二次電池。 - 前記上蓋及び底蓋を形成するセラミックはα-アルミナであり、前記正極活物質収納容器は、一端を前記上蓋又は前記底蓋に固定され前記正極室内を軸方向に延びる陽極棒を有する請求項10記載の固体電解質二次電池。
- 前記陽極棒は、径方向に放射状に延出し前記正極室を複数の区画に形成する板状の間隔片
を有する請求項11記載の固体電解質二次電池。 - 前記軟質シートは、金属箔である請求項10記載の固体電解質二次電池。
- 前記負極部材は軟質シートで形成され、さらに前記負極室内には前記負極部材の外側面に
作用する圧力を前記筒状壁の外周面に及ぼす多孔質スペーサーを備える請求項10記載の固体電解質二次電池。 - 前記多孔質スペーサーを構成する多孔質材は、金属繊維、発泡金属又は多孔質セラミック
である請求項14記載の固体電解質二次電池。 - 前記負極活物質はナトリウムであり、前記正極物質は硫黄である請求項1記載の固体電解質二次電池。
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/699,697 US20130065102A1 (en) | 2010-05-25 | 2011-05-25 | Solid electrode secondary battery |
CN2011800257284A CN102906929A (zh) | 2010-05-25 | 2011-05-25 | 固体电解质二次电池 |
RU2012156269/07A RU2522173C1 (ru) | 2010-05-25 | 2011-05-25 | Аккумуляторная батарея с твердым электродом |
BR112012029758A BR112012029758A2 (pt) | 2010-05-25 | 2011-05-25 | bateria secundária de eletrólito sólido |
EP11786334.0A EP2579379A4 (en) | 2010-05-25 | 2011-05-25 | SOLID ELECTROLYTE SECONDARY BATTERY |
JP2012517142A JP5546063B2 (ja) | 2010-05-25 | 2011-05-25 | 固体電解質二次電池 |
KR1020127033383A KR101504985B1 (ko) | 2010-05-25 | 2011-05-25 | 고체 전해질 2차 전지 |
ZA2012/08831A ZA201208831B (en) | 2010-05-25 | 2012-11-22 | Solid electrode secondary battery |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010119415 | 2010-05-25 | ||
JP2010-119415 | 2010-05-25 | ||
JP2010149310 | 2010-06-30 | ||
JP2010-149310 | 2010-06-30 | ||
JP2010213743 | 2010-09-24 | ||
JP2010-213743 | 2010-09-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011148631A1 true WO2011148631A1 (ja) | 2011-12-01 |
Family
ID=45003630
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/002914 WO2011148631A1 (ja) | 2010-05-25 | 2011-05-25 | 固体電解質二次電池 |
Country Status (9)
Country | Link |
---|---|
US (1) | US20130065102A1 (ja) |
EP (1) | EP2579379A4 (ja) |
JP (1) | JP5546063B2 (ja) |
KR (1) | KR101504985B1 (ja) |
CN (1) | CN102906929A (ja) |
BR (1) | BR112012029758A2 (ja) |
RU (1) | RU2522173C1 (ja) |
WO (1) | WO2011148631A1 (ja) |
ZA (1) | ZA201208831B (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014192253A1 (ja) * | 2013-05-27 | 2014-12-04 | Ohkawa Hiroshi | 燃料型固体電解質二次電池 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6732218B2 (ja) * | 2015-10-06 | 2020-07-29 | 有限会社中勢技研 | ナトリウム−硫黄電池 |
CN105390756B (zh) * | 2015-11-23 | 2018-01-12 | 中国东方电气集团有限公司 | 一种安全钠硫电池 |
JP6276305B2 (ja) * | 2015-11-24 | 2018-02-07 | 有限会社中勢技研 | 溶融ナトリウム電池及び溶融ナトリウム電池用隔壁 |
KR102175830B1 (ko) | 2016-02-25 | 2020-11-06 | 주식회사 엘지화학 | 음극활물질 조성물, 이의 제조 방법 및 이를 포함하는 리튬 이차전지용 음극 |
CN108987814A (zh) * | 2018-07-28 | 2018-12-11 | 江西睿达新能源科技有限公司 | 一种锂离子电池用镍钴锰三元正极材料 |
JP7261995B2 (ja) * | 2019-01-30 | 2023-04-21 | パナソニックIpマネジメント株式会社 | 全固体電池およびその製造方法 |
RU2722502C1 (ru) * | 2019-10-30 | 2020-06-01 | ООО "Нординкрафт Сервис" | Электрический аккумулятор |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5033420A (ja) * | 1973-07-30 | 1975-03-31 | ||
JPS5038030A (ja) * | 1973-08-11 | 1975-04-09 | ||
JPS5538030A (en) | 1978-09-11 | 1980-03-17 | Hitachi Ltd | Semiconductor device |
JPS6366863A (ja) | 1986-09-08 | 1988-03-25 | Ngk Insulators Ltd | ナトリウム−硫黄電池 |
JPS63271865A (ja) | 1987-04-30 | 1988-11-09 | Tokyo Electric Power Co Inc:The | ナトリウム−硫黄電池 |
JPH02112168A (ja) | 1988-10-20 | 1990-04-24 | Ngk Insulators Ltd | ナトリウム一硫黄電池 |
JPH03187160A (ja) | 1989-12-15 | 1991-08-15 | Ngk Insulators Ltd | ナトリウムー硫黄電池 |
JPH06196204A (ja) | 1992-10-29 | 1994-07-15 | Ngk Insulators Ltd | ナトリウム−硫黄電池における固体電解質管と絶縁リングとの接合構造及びナトリウム−硫黄電池 |
JPH07176328A (ja) | 1993-12-21 | 1995-07-14 | Mitsubishi Heavy Ind Ltd | ナトリウム系二次電池 |
JPH10302830A (ja) | 1997-04-28 | 1998-11-13 | Mitsubishi Heavy Ind Ltd | ナトリウム/溶融塩二次電池及びその組立方法 |
JPH11121031A (ja) | 1997-10-17 | 1999-04-30 | Mitsubishi Heavy Ind Ltd | ベータアルミナ電解質構造体及び二次電池 |
JP2001093570A (ja) | 1999-08-25 | 2001-04-06 | Bi Patent Holding Sa | 電気化学電池セパレータ |
JP2001102087A (ja) | 1999-08-25 | 2001-04-13 | Bi Patent Holding Sa | 電気化学電池セパレータ |
JP2001243975A (ja) | 2000-02-28 | 2001-09-07 | Hitachi Ltd | ナトリウム硫黄電池、その使用方法及びそれを用いたモジュ−ル |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3915741A (en) * | 1973-07-30 | 1975-10-28 | Toyoda Chuo Kenkyusho Kk | Sodium-sulfur cell with improved separator |
US4124739A (en) * | 1974-11-28 | 1978-11-07 | Chloride Silent Power Ltd. | Alkali metal-sulphur cells |
GB1511152A (en) * | 1975-04-24 | 1978-05-17 | Chloride Silent Power Ltd | Alkali metal-sulphur cells |
GB1530273A (en) * | 1976-06-25 | 1978-10-25 | Atomic Energy Authority Uk | Electric cells having a liquid anode and a liquid cathode |
US4055710A (en) * | 1976-10-01 | 1977-10-25 | Chloride Silent Power Limited | Electrochemical cells having solid electrolyte of tubular form |
US4226923A (en) * | 1979-10-29 | 1980-10-07 | Ford Motor Company | Volume efficient sodium sulfur battery |
DE3117384A1 (de) * | 1981-05-02 | 1982-12-16 | Brown, Boveri & Cie Ag, 6800 Mannheim | "elektrochemische speicherzelle" |
RU2070756C1 (ru) * | 1994-04-21 | 1996-12-20 | Юшина Людмила Дмитриевна | Аккумулятор с твердым электролитом |
JPH0837023A (ja) * | 1994-07-22 | 1996-02-06 | Hitachi Ltd | ナトリウム−硫黄電池 |
RU2295178C2 (ru) * | 2005-04-21 | 2007-03-10 | Общество с ограниченной ответственностью "Высокоэнергетические батарейные системы" (ООО "ВЭБС") | Твердотельный вторичный источник тока |
RU2313158C2 (ru) * | 2006-01-10 | 2007-12-20 | Общество С Ограниченной Ответственностью "Высокоэнергетические Батарейные Системы" | Твердотельный химический источник тока и способ повышения разрядной мощности |
CN102906930B (zh) * | 2010-05-31 | 2016-09-14 | 大川宏 | 固体电解质二次电池 |
-
2011
- 2011-05-25 CN CN2011800257284A patent/CN102906929A/zh active Pending
- 2011-05-25 BR BR112012029758A patent/BR112012029758A2/pt not_active IP Right Cessation
- 2011-05-25 US US13/699,697 patent/US20130065102A1/en not_active Abandoned
- 2011-05-25 KR KR1020127033383A patent/KR101504985B1/ko not_active IP Right Cessation
- 2011-05-25 EP EP11786334.0A patent/EP2579379A4/en not_active Withdrawn
- 2011-05-25 JP JP2012517142A patent/JP5546063B2/ja not_active Expired - Fee Related
- 2011-05-25 WO PCT/JP2011/002914 patent/WO2011148631A1/ja active Application Filing
- 2011-05-25 RU RU2012156269/07A patent/RU2522173C1/ru not_active IP Right Cessation
-
2012
- 2012-11-22 ZA ZA2012/08831A patent/ZA201208831B/en unknown
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5033420A (ja) * | 1973-07-30 | 1975-03-31 | ||
JPS5038030A (ja) * | 1973-08-11 | 1975-04-09 | ||
JPS5538030A (en) | 1978-09-11 | 1980-03-17 | Hitachi Ltd | Semiconductor device |
JPS6366863A (ja) | 1986-09-08 | 1988-03-25 | Ngk Insulators Ltd | ナトリウム−硫黄電池 |
JPS63271865A (ja) | 1987-04-30 | 1988-11-09 | Tokyo Electric Power Co Inc:The | ナトリウム−硫黄電池 |
JPH02112168A (ja) | 1988-10-20 | 1990-04-24 | Ngk Insulators Ltd | ナトリウム一硫黄電池 |
JPH03187160A (ja) | 1989-12-15 | 1991-08-15 | Ngk Insulators Ltd | ナトリウムー硫黄電池 |
JPH06196204A (ja) | 1992-10-29 | 1994-07-15 | Ngk Insulators Ltd | ナトリウム−硫黄電池における固体電解質管と絶縁リングとの接合構造及びナトリウム−硫黄電池 |
JPH07176328A (ja) | 1993-12-21 | 1995-07-14 | Mitsubishi Heavy Ind Ltd | ナトリウム系二次電池 |
JPH10302830A (ja) | 1997-04-28 | 1998-11-13 | Mitsubishi Heavy Ind Ltd | ナトリウム/溶融塩二次電池及びその組立方法 |
JPH11121031A (ja) | 1997-10-17 | 1999-04-30 | Mitsubishi Heavy Ind Ltd | ベータアルミナ電解質構造体及び二次電池 |
JP2001093570A (ja) | 1999-08-25 | 2001-04-06 | Bi Patent Holding Sa | 電気化学電池セパレータ |
JP2001102087A (ja) | 1999-08-25 | 2001-04-13 | Bi Patent Holding Sa | 電気化学電池セパレータ |
JP2001243975A (ja) | 2000-02-28 | 2001-09-07 | Hitachi Ltd | ナトリウム硫黄電池、その使用方法及びそれを用いたモジュ−ル |
Non-Patent Citations (1)
Title |
---|
See also references of EP2579379A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014192253A1 (ja) * | 2013-05-27 | 2014-12-04 | Ohkawa Hiroshi | 燃料型固体電解質二次電池 |
Also Published As
Publication number | Publication date |
---|---|
KR20130040921A (ko) | 2013-04-24 |
EP2579379A4 (en) | 2015-08-05 |
US20130065102A1 (en) | 2013-03-14 |
BR112012029758A2 (pt) | 2017-03-07 |
JPWO2011148631A1 (ja) | 2013-07-25 |
EP2579379A1 (en) | 2013-04-10 |
JP5546063B2 (ja) | 2014-07-09 |
ZA201208831B (en) | 2013-09-25 |
KR101504985B1 (ko) | 2015-03-23 |
CN102906929A (zh) | 2013-01-30 |
RU2012156269A (ru) | 2014-06-27 |
RU2522173C1 (ru) | 2014-07-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5546063B2 (ja) | 固体電解質二次電池 | |
CN110828746B (zh) | 一种电池包和电动车 | |
US9728827B2 (en) | Battery pack | |
US7544440B2 (en) | Secondary battery having a sealing gasket with concave and convex portions | |
US4800143A (en) | High-temperature storage battery | |
US3975210A (en) | Metal-gas battery with axial reactant gas storage cavity | |
US4038462A (en) | Solid-electrolyte battery, particularly for the storage of electrical energy | |
CN111630704B (zh) | 电解质元件和结合有电解质元件的电池 | |
US4957830A (en) | Rechargeable metal oxide-hydrogen battery | |
WO2011152028A1 (ja) | 固体電解質二次電池 | |
CN108463899B (zh) | 用于储存电能的装置以及用于其组装和启动以及用于其操作的方法 | |
JPH05217608A (ja) | 金属酸化物水素電池 | |
CN212625802U (zh) | 一种电池包和电动车 | |
WO2012031346A1 (en) | Bi-polar electrochemical cell | |
CN108292784B (zh) | 熔融钠电池以及熔融钠电池用隔壁 | |
CN115715439A (zh) | 二次电池 | |
KR100649568B1 (ko) | 이차 전지 | |
US20200006813A1 (en) | High temperature batteries | |
JP2021009795A (ja) | 蓄電モジュール | |
WO2017090636A1 (ja) | 溶融ナトリウム電池及び溶融ナトリウム電池用隔壁 | |
US20240258632A1 (en) | Battery pack | |
JP7170576B2 (ja) | 電気化学素子及び電気化学素子の製造方法 | |
KR101557489B1 (ko) | 나트륨 유황 전지 | |
JPH04298967A (ja) | 燃料電池 | |
JP6043099B2 (ja) | 電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180025728.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11786334 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2012517142 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 9703/DELNP/2012 Country of ref document: IN |
|
REEP | Request for entry into the european phase |
Ref document number: 2011786334 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011786334 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13699697 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1201006097 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20127033383 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2012156269 Country of ref document: RU Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012029758 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012029758 Country of ref document: BR Kind code of ref document: A2 Effective date: 20121122 |