WO2011152028A1 - 固体電解質二次電池 - Google Patents
固体電解質二次電池 Download PDFInfo
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- WO2011152028A1 WO2011152028A1 PCT/JP2011/003022 JP2011003022W WO2011152028A1 WO 2011152028 A1 WO2011152028 A1 WO 2011152028A1 JP 2011003022 W JP2011003022 W JP 2011003022W WO 2011152028 A1 WO2011152028 A1 WO 2011152028A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—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
- H01M10/04—Construction or manufacture in general
- H01M10/0468—Compression means for stacks of electrodes and separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—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
- H01M10/3954—Sodium-sulfur cells containing additives or special arrangement in the sulfur compartment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4214—Arrangements for moving electrodes or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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.
- the sodium-sulfur battery includes a positive electrode chamber that stores molten sulfur that is a positive electrode active material, a negative electrode chamber that stores molten sodium that is a negative electrode active material, and a molten sulfur located between the positive electrode chamber and the negative electrode chamber. And a solid electrolyte in the form of a wall made of a material such as ⁇ -alumina that isolates molten sodium and is permeable to sodium ions.
- molten sulfur as the positive electrode active material and sodium polysulfide as the reaction product have a high specific gravity, and thus tended to accumulate in the lower part of the positive electrode chamber due to their own weight. For this reason, these substances cannot fully participate in the charge / discharge reaction, and the utilization factor of the active material is reduced.
- Japanese Patent Laid-Open No. 5-266921 discloses that the shape of the positive electrode chamber formed on the outer peripheral side of the test tubular ⁇ -alumina partition containing molten sulfur as the positive electrode active material is lower in the horizontal direction.
- a sodium sulfur battery formed to have a small cross-sectional area is disclosed.
- the sodium ratio of sodium polysulfide in the lower part of the positive electrode chamber is made lower than that in the upper part during charging, and sodium sulfide having a high sodium ratio is prevented from concentrating in the lower part of the positive electrode chamber.
- Japanese Patent Laid-Open No. 6-89739 discloses a sodium sulfur battery in which the lower bulk density of the positive electrode conductive material impregnated with molten sulfur is made higher than the upper bulk density.
- an active material such as sodium polysulfide reacts quickly in the lower portion, the utilization factor of the active material in the lower portion is improved, and the phenomenon that sodium polysulfide is accumulated in the lower portion can be prevented.
- sodium sulfur batteries are attracting attention as power storage because they have the ability to store large amounts of power.
- An example of a method for increasing the battery capacity of a sodium-sulfur battery is JP-A-2004-177891.
- a method is disclosed in which the battery capacity is increased by increasing the packing density of molten sulfur that is a positive electrode active material and molten sodium that is a negative electrode active material.
- the volume of the positive electrode chamber containing the molten sulfur as the positive electrode active material and the negative electrode chamber containing the molten sodium as the negative electrode active material are constant. There is a limit to increasing the battery capacity.
- the volume of the storage chamber itself in which the active material is stored is increased, a large amount of active material can be stored.
- the volume of the storage chamber is increased, the area acting as a partition wall of the solid electrolyte in contact with the active material is relatively reduced, so that the battery reaction is lowered.
- the storage chamber is a space partitioned by a solid electrolyte, storing a large amount of active material therein has a problem from the viewpoint of safety.
- molten sodium is stored in a sodium storage container at a position apart from the solid electrolyte, and the sodium is provided in the plate-shaped solid electrolyte from the storage container.
- the first aspect of the present invention is to provide a higher performance solid electrolyte secondary battery by suppressing the deterioration of the positive electrode active material of the solid electrolyte secondary battery.
- a second object of the present invention is to provide a solid electrolyte secondary battery having a larger battery capacity.
- a third object is to provide a solid electrolyte secondary battery capable of obtaining a large output while ensuring a large battery capacity and improving the battery performance.
- the solid electrolyte secondary battery of the present invention includes a positive electrode chamber containing at least a positive electrode active material, a negative electrode chamber containing at least a negative electrode active material, and the positive electrode active material positioned between the positive electrode chamber and the negative electrode chamber.
- a secondary battery comprising a wall-shaped solid electrolyte that isolates a material from the negative electrode active material and has conductivity with respect to the negative electrode active material, wherein the secondary battery is independent of the positive electrode chamber and includes at least one of the positive electrode active materials.
- a positive electrode active material container for storing a part thereof; Passage means for circulating and moving the positive electrode active material in one direction from the positive electrode chamber to the positive electrode active material container and from the positive electrode active material container to the positive electrode chamber.
- a positive electrode active material container for storing a part of the positive electrode active material is provided independently of the positive electrode chamber, and the positive electrode active material is placed in one direction between the positive electrode chamber and the auxiliary chamber. Passage means for circulating movement is provided. Thereby, the positive electrode active material accommodated in the positive electrode chamber is circulated again into the positive electrode chamber through the positive electrode active material container by the passage means. That is, the positive electrode active material accommodated in the positive electrode chamber moves. For this reason, the phenomenon in which the positive electrode active material concentrates and accumulates in the lower part of the positive electrode chamber can be suppressed. Moreover, since the positive electrode active material circulates in one direction, the concentration of the positive electrode active material in the positive electrode chamber can be kept substantially uniform. Therefore, the active material can be used efficiently, and the battery performance can be improved.
- the positive electrode active material refers to a material that reacts with a negative electrode active material typified by sulfur to form a compound.
- the negative electrode active material is a metal typified by sodium, and lithium, potassium, and the like are also candidates.
- the wall-shaped solid electrolyte is made of a material such as ⁇ -alumina, ⁇ "alumina, or other ceramics, and functions as a partition that separates the positive electrode active material from the negative electrode active material and allows the negative electrode active material to permeate. Therefore, the shape of the solid electrolyte is not particularly limited, and may be a container-shaped body having a positive electrode chamber in which the positive electrode active material is accommodated and a negative electrode chamber in which the negative electrode active material is accommodated in the internal space.
- the positive electrode active material container independent of the positive electrode chamber means that the pressure in the positive electrode chamber fluctuates due to battery discharge and charge when the positive electrode active material or gas does not move between the positive electrode active material container and the positive electrode active material container. It means that it does not cause a large pressure fluctuation.
- the positive electrode active material container can be provided in the inner wall that defines the positive electrode chamber, or can be provided at a position completely different from the portion that defines the positive electrode chamber.
- the passage means means a continuous internal space through which the positive electrode active material can pass.
- the passage means includes a first passage having a first one-way valve for moving the positive electrode active material from the positive electrode chamber to the positive electrode active material container, and a second one-way valve for moving the positive electrode active material from the positive electrode active material container to the positive electrode chamber. It is preferable to provide the 2nd channel
- the one-way valve has a function of always keeping a fluid flow in a certain direction and preventing backflow.
- the one-way valve may be, for example, a valve that is opened by a fluid pressure and closed by a back pressure when backflowing.
- the ionized negative electrode active material moves from the negative electrode chamber to the positive electrode chamber, so the amount of active material increases in the positive electrode chamber, and the liquid level of the active material in the positive electrode chamber gradually increases. To do. Therefore, the pressure in the positive electrode chamber, which is a sealed space, gradually increases. Therefore, the pressure in the positive electrode chamber becomes higher than the pressure in the positive electrode active material container, and the first one-way valve is opened by the pressure difference. Thereafter, the positive electrode active material moves from the positive electrode chamber to the positive electrode active material container through the first passage. At this time, since the second one-way valve does not open in the direction in which the positive electrode active material flows from the positive electrode chamber to the positive electrode active material container, the positive electrode active material does not move through the second passage.
- the pressure in the positive electrode chamber which is a sealed space, gradually decreases.
- the liquid level in the positive electrode active material container is raised by the positive electrode active material moved from the positive electrode chamber due to the reaction during discharge, the pressure in the positive electrode active material container, which is also a sealed space, is high. Therefore, the pressure in the positive electrode active material container auxiliary chamber becomes higher than the pressure in the positive electrode chamber, and the second one-way valve is opened by the pressure difference.
- the positive electrode active material moves from the positive electrode active material container auxiliary chamber to the positive electrode chamber through the second passage.
- the first one-way valve does not open in the direction in which the positive electrode active material flows from the positive electrode active material container to the positive electrode chamber, the positive electrode active material does not move through the first passage.
- the passage means has a simple structure and can easily circulate and move the positive electrode active material in one direction.
- the inlet of one of the first passage and the second passage is disposed in the upper portion of the positive electrode chamber and the outlet is disposed in the upper portion of the positive electrode active material container, and the other passage of the first passage and the second passage.
- the inlet is preferably disposed at the lower portion of the positive electrode active material container and the outlet is disposed at the lower portion of the positive electrode chamber.
- the solid electrolyte secondary battery of the present invention may be provided with moving means for circulating and moving the positive electrode active material in one direction from the positive electrode chamber to the positive electrode active material container and further from the positive electrode active material container to the positive electrode chamber.
- moving means for circulating and moving the positive electrode active material in one direction from the positive electrode chamber to the positive electrode active material container and further from the positive electrode active material container to the positive electrode chamber.
- a control means adjusts the quantity and speed
- the control means is, for example, an electronic control device having a storage unit, an input / output unit, etc. in addition to a calculation unit that performs calculation and control, and performs the above control based on the measurement result of a measuring instrument such as a flow sensor. Can be used.
- the container shape body of the solid electrolyte means one having a shape in which the space defined by the inner wall surface of the solid electrolyte is an accommodation space. If a lid and a bottom, or a lid or a bottom is provided in the space defined by the inner wall surface of the container-shaped body, a sealed section is formed and a liquid storage space, that is, a positive electrode chamber and a negative electrode chamber. Note that both the positive electrode chamber and the negative electrode chamber may have a hole shape extending in the axial direction. Further, the container-shaped body having the hole-shaped positive electrode chamber and the negative electrode chamber may have a columnar body as the outer shape. Here, the columnar body refers to a shape extending in a uniaxial direction.
- the outer peripheral shape may be an arbitrary shape such as a circle, an ellipse, a triangle, or a quadrangle.
- the columnar body may have at least one positive electrode chamber extending in the axial direction.
- the cross-sectional shape of the positive electrode chamber can be an arbitrary shape such as a circle, an ellipse, a triangle, or a quadrangle. Since this columnar body extends in the axial direction, the shape is simple and manufacture is easy.
- the negative electrode chamber may extend in the axial direction along the wall surface of the positive electrode chamber and be spaced apart from the wall surface, and the cross section may be formed inside the columnar body 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 each negative electrode chamber and the positive electrode chamber mainly functions as an electrolyte.
- a biasing member that abuts on the outer surface of the solid electrolyte container-shaped body and presses the outer peripheral surface.
- This urging member can be formed, for example, by compressing heat-resistant carbon fiber, glass fiber or the like into a thinner mat shape.
- the present invention preferably includes a negative electrode active material container that communicates with the negative electrode chamber and sends and receives the negative electrode active material. It is preferable to store most of the negative electrode active material in this negative electrode active material container, and to reduce the amount of the negative electrode active material stored in the negative electrode chamber of the container-shaped body. By using the negative electrode active material container, most of the negative electrode active material and the positive electrode active material can be kept away from each other, and safety is increased. Further, since a large amount of the negative electrode active material can be stored in the negative electrode active material container, the battery capacity can be increased.
- FIG. 1 is a longitudinal sectional view of a sodium sulfur battery of Example 1.
- FIG. 3 is a longitudinal sectional view of a sodium sulfur battery of Example 2.
- FIG. It is sectional drawing of a non-return valve.
- 4 is a longitudinal sectional view of a sodium sulfur battery of Example 3.
- FIG. It is a cross-sectional view of a sodium-sulfur battery using a second cylindrical body formed of a solid electrolyte.
- It is a cross-sectional view of a sodium-sulfur battery using a third cylindrical body formed of a solid electrolyte.
- 6 is a longitudinal sectional view of a sodium sulfur battery of Example 4.
- FIG. 6 is a longitudinal sectional view of a sodium sulfur battery of Example 5.
- FIG. 7 is a side cross-sectional view of a main part of a sodium sulfur battery of Example 6.
- FIG. 1 is a longitudinal sectional view of a sodium-sulfur battery 1 of Example 1 of the present invention
- FIG. 3 is a sectional view of a check valve.
- the sodium-sulfur battery 1 includes a metal bottomed cylindrical positive electrode container 11, a bottomed cylindrical solid electrolyte tube 15 disposed inside the positive electrode container 11 and made of ⁇ -alumina, and a solid electrolyte tube 15.
- a bottomed cylindrical negative electrode container 13 provided with a small hole 12 at the bottom thereof, and a metal bottomed cylindrical auxiliary container 10 integrally disposed at the lower end of the positive electrode container 11.
- the metal supply pipe 20 and the recovery pipe 21 extending in the axial direction are the main components.
- the auxiliary container 10 constitutes the positive electrode active material container of the present invention.
- the molten sulfur 16 is accommodated in the positive electrode chamber 18 which is defined by the inner peripheral surface side of the positive electrode container 11 and the outer peripheral surface side of the solid electrolyte 15 and is formed as a sealed space as described below.
- Molten sodium 14 is stored.
- a part of molten sulfur 16 is stored in an auxiliary chamber 17 formed as a sealed space by the bottom of the auxiliary container 10 and the positive electrode container 11.
- the supply pipe 20 penetrates the bottom of the positive electrode container 11 and is welded at the penetrated portion to communicate the positive electrode chamber 18 and the auxiliary chamber 17.
- One end is disposed at the lower portion of the auxiliary chamber 17 and the other end The part is disposed in the lower part of the positive electrode chamber 18.
- a check valve 201 is provided in the supply pipe 20 so that the direction in which the molten sulfur 16 flows from the lower portion of the auxiliary chamber 17 to the lower portion of the positive electrode chamber 18 is one direction.
- the lower part and the lower part of the positive electrode chamber 18 serve as an inlet and an outlet of the supply pipe 20, respectively.
- the recovery tube 21 penetrates the bottom of the positive electrode container 11 and is welded at the penetrated portion to communicate the positive electrode chamber 18 and the auxiliary chamber 17.
- One end is disposed on the upper portion of the positive electrode chamber 18, and the other end The part is disposed in the upper part of the auxiliary chamber 17.
- a check valve 211 is provided inside the recovery pipe 21 so that the molten sulfur 16 flows in one direction from the upper part of the positive electrode chamber 18 to the lower part of the auxiliary chamber 17.
- the upper part serves as an inlet and an outlet of the recovery pipe 21, respectively.
- the check valve 211 is the same as that shown in FIG.
- the positive electrode container 11 and the solid electrolyte tube 15 are coupled via an insulating ring 22 and a positive electrode fitting 23. Thereby, the positive electrode chamber 18 becomes a sealed space.
- a negative electrode fitting 24 is joined to the upper end surface of the insulating ring 22, and a negative electrode lid 25 is welded and fixed to the negative electrode fitting 24.
- a positive electrode terminal 26 and a negative electrode terminal 27 are provided on the outer periphery of the positive electrode container 11 and the upper surface of the negative electrode lid 25, respectively.
- a bottomed cylindrical safety tube 28 is provided outside the negative electrode container 13 and inside the solid electrolyte tube 15. In the sodium-sulfur battery 1, during discharge, the molten sodium 14 in the negative electrode container 13 is supplied into the safety tube 28 through the small holes 12, the safety tube 28 is filled with the supplied molten sodium 14, and the solid electrolyte tube 15. And the safety tube 28 are supplied into the negative electrode chamber 19.
- the molten sodium 14 in the negative electrode chamber 19 becomes sodium ions, passes through the solid electrolyte tube 15 and moves into the positive electrode chamber 18, contacts with the molten sulfur 16 and discharges to generate sodium sulfide.
- sodium sulfide in the positive electrode chamber 18 decomposes into sodium ions and molten sulfur 16, and the sodium ions pass through the solid electrolyte tube 15 and move into the negative electrode chamber 19 to generate molten sodium 14. Returned to the container 13.
- the ionized molten sodium 14 moves from the negative electrode chamber 19 to the positive electrode chamber 18, and the amount of sodium sulfide increases in the positive electrode chamber 18, so that the liquid level in the positive electrode chamber 18 gradually increases. To rise.
- the pressure in the positive electrode chamber 18 that is a sealed space gradually increases. Therefore, the pressure on the positive electrode chamber 18 side becomes higher than the pressure on the auxiliary chamber 17 side, and the check valve 211 in the recovery pipe 21 is opened by the pressure difference. Thereafter, the molten sulfur 16 moves from the positive electrode chamber 18 to the auxiliary chamber 17 through the recovery pipe 21. At this time, the check valve 201 in the supply pipe 20 does not open in the direction in which the molten sulfur 16 flows from the positive electrode chamber 18 to the auxiliary chamber 17, so that the molten sulfur 16 does not move through the supply pipe 20. .
- the ionized molten sodium 14 moves from the positive electrode chamber 18 to the negative electrode chamber 19, so that the amount of sodium polysulfide decreases in the positive electrode chamber 18 and the liquid level in the positive electrode chamber 18 gradually decreases. . Therefore, the pressure in the positive electrode chamber 18 that is a sealed space gradually decreases.
- the pressure in the auxiliary chamber 17 that is also a sealed space is high. Therefore, the pressure on the auxiliary chamber 17 side becomes higher than the pressure on the positive electrode chamber 18 side, and the check valve 201 in the supply pipe 20 is opened by the pressure difference.
- the molten sulfur 16 moves from the auxiliary chamber 17 to the positive electrode chamber 18 through the supply pipe 20.
- the check valve 211 in the recovery pipe 21 does not open in the direction in which the molten sulfur 16 flows from the auxiliary chamber 17 to the positive electrode chamber 18, so that the molten sulfur 16 does not move through the recovery pipe 21. . Since the molten sulfur 16 circulates and moves in this way, the phenomenon that sodium polysulfide concentrates and accumulates in the lower part of the positive electrode chamber 18 can be suppressed. Further, since the molten sulfur 16 circulates and moves in one direction, the concentration of the molten sulfur 16 in the positive electrode chamber 18 can be kept substantially uniform. Therefore, the active material can be used efficiently, and the battery performance can be improved.
- the longitudinal cross-sectional view of the sodium sulfur battery 2 of Example 2 of this invention is shown in FIG.
- the sodium-sulfur battery 2 includes a metal cylindrical protective can 31, a sodium container 33 held on an upper portion in the space of the protective can 31 via an insulator 32 formed of a glass fiber mat, A cylindrical body 35 made of ⁇ -alumina held in the lower part of the space of the protective can 31 and a metal bottomed cylindrical auxiliary container 30 integrally disposed at the lower end of the protective can 31 A metal supply pipe 40 and a recovery pipe 41 extending in the axial direction are main components.
- the auxiliary container 30 constitutes the positive electrode active material container of the present invention.
- the cylindrical body 35 has a thick cylindrical shape, and the internal space corresponding to the shaft hole becomes the positive electrode chamber 18.
- a large number of pore-shaped negative electrode chambers 49 extending in the axial direction with a slight gap along the inner peripheral surface of the cylindrical body 35 are formed at intervals in the circumferential direction.
- the positive electrode chamber 48 is formed as a sealed space as described below, and the molten sulfur 16 is accommodated in the chamber. Further, molten sodium 14 is stored in the sodium container 33, and part of the molten sulfur 16 is stored in the positive electrode chamber 18 formed as a sealed space by the bottom cover 311 that is the bottom of the auxiliary container 30 and the protective can 31. ing.
- the supply pipe 40 penetrates the bottom lid 311 and is welded at the penetrated portion to communicate the positive electrode chamber 18 and the inside of the auxiliary container 30, and one end portion is disposed at the lower part in the auxiliary container 30, and the other end.
- the part is disposed in the lower part of the positive electrode chamber 18.
- a check valve 401 is provided inside the supply pipe 40 so that the direction in which the molten sulfur 16 flows from the lower part in the auxiliary container 30 to the lower part of the positive electrode chamber 48, and the lower part in the auxiliary container 30 and the positive electrode chamber are provided.
- the lower part of 18 is an inlet and an outlet of the supply pipe 40, respectively.
- the recovery pipe 41 penetrates the bottom lid 311 and is welded at the penetrated portion to communicate the positive electrode chamber 18 and the auxiliary container 30, with one end disposed at the upper portion of the positive electrode chamber 18 and the other end.
- the part is disposed in the upper part of the auxiliary container 30.
- a check valve 411 is provided inside the recovery pipe 41 so that the direction in which the molten sulfur 16 flows from the upper part of the positive electrode chamber 18 to the lower part of the auxiliary container 30 is one direction, and the upper part of the positive electrode chamber 18 and the auxiliary container 30 are provided.
- the upper part becomes the inlet and outlet of the recovery pipe 41, respectively.
- An upper lid 351 made of ⁇ -alumina is integrally bonded and fixed to the upper end surface of the cylindrical body 35 with a glass adhesive or the like.
- the upper lid 351 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 cylindrical body 35 to form a ring-shaped passage 352.
- the ring-shaped passage 352 communicates with the upper end openings of all the negative electrode chambers 49 of the cylindrical body 35.
- a vertical passage 353 extending from the upper surface of the upper lid 351 to the ring-shaped passage 352 is provided.
- a sealing ring 355 made of ⁇ -alumina is integrally bonded and fixed to the lower end surface of the cylindrical body 35 with a glass adhesive or the like.
- a sodium container 33 is disposed on the upper lid 351.
- a through hole is formed in the bottom of the sodium container 33, and a metal connecting pipe 354 having an axial hole is inserted and joined to the through hole and a vertical passage 353 that is a common hole with the through hole.
- Molten sodium 14 is held in the sodium container 33, and the molten sodium 14 passes through the shaft hole of the connection pipe 354, the vertical passage 353, and the ring-shaped passage 352, flows into all the negative electrode chambers 49, and fills the negative electrode chamber 49. become.
- an urging member 37 made of a carbon fiber mat is stored in the protective can 31 in a state compressed in the thickness direction.
- a current collector 38 made of a carbon fiber aggregate impregnated with molten sulfur 16 is inserted into the positive electrode chamber 18 formed in the cylindrical body 35. Further, a metal recovery pipe 41 is located at the central portion of the current collector 38 and functions as an anode.
- a metal bottom cover 311 is joined to the lower end surface of the cylindrical body 35 with a glass adhesive.
- the positive electrode chamber 18 is formed as a sealed space.
- the bottom lid 311 is welded to the side peripheral portion of the protective can 31 and becomes the bottom portion of the protective can 31.
- a negative electrode terminal 37 is joined to the sodium container 33, and an upper portion thereof protrudes upward through a through hole of the protective can 31.
- a positive electrode terminal 36 is joined to the upper side of the protective can 31.
- the molten sodium 14 in the negative electrode chamber 49 becomes sodium ions, passes through the portion that forms the solid electrolyte partition of the cylindrical body 35, moves to the positive electrode chamber 18, and contacts with the molten sulfur 16. And discharge to produce sodium sulfide.
- the same amount of molten sodium 14 moved from the negative electrode chamber 49 to the positive electrode chamber 18 by discharge is replenished from the molten sodium 14 accommodated in the sodium container 13. Therefore, at the time of discharge, the molten sodium 14 in the sodium container 33 decreases, and the sodium sulfide in the positive electrode chamber 18 increases.
- the molten sulfur 16 circulates in the positive electrode chamber 18 and the auxiliary vessel 30 through the recovery pipe 41 and the supply pipe 40 due to the pressure difference between the positive electrode chamber 18 and the auxiliary vessel 30 during charging and discharging. Moving.
- Such a circulating movement of the molten sulfur 16 can suppress a phenomenon in which sodium polysulfide is concentrated and accumulated in the lower portion of the positive electrode chamber 18. Further, since the molten sulfur 16 circulates and moves in one direction, the concentration of the molten sulfur 16 in the positive electrode chamber 18 can be kept substantially uniform. Therefore, the active material can be used efficiently, and the battery performance can be improved.
- the longitudinal cross-sectional view of the sodium sulfur battery 1 of Example 3 of this invention is shown in FIG.
- 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, A cylindrical body 15 made of ⁇ -alumina held in the lower part of the space of the protective can 11 and a metallic bottomed cylindrical sulfur container 30 integrally disposed at the lower end of the protective can 11.
- the control device 130 is a main component.
- the cylindrical body 15 has a thick cylindrical shape, and the internal space corresponding to the shaft hole becomes the positive electrode chamber 18.
- a large number of pore-shaped negative electrode chambers 19 extending in the axial direction with a slight gap along the inner peripheral surface of the cylindrical body 15 are formed at intervals in the circumferential direction.
- the positive electrode chamber 18 is formed as a sealed space as described below, and the molten sulfur 16 is accommodated in the chamber.
- the molten sodium 14 is stored in the sodium container 13, and the molten sulfur 16 is partially stored in the sulfur container 30.
- the supply pipe 100 includes a first supply pipe part 101 that connects the sulfur container 16 and the pump 120, and a second supply pipe part 102 that connects the pump 120 and the positive electrode chamber 18.
- the first supply pipe portion 101 has an inlet disposed at the lower portion of the sulfur container 30, penetrates the side surface of the protective can 11, is welded at the penetrated portion, and communicates with the pump 120 at the tip.
- the second supply pipe portion 102 has an outlet disposed at the lower portion of the positive electrode chamber 18, penetrates the bottom lid 111, is welded at the penetrated portion, and further penetrates the side surface of the protective can 11, and the penetrated portion. And is communicated with the pump 120 at the end.
- the recovery pipe 110 penetrates the bottom lid 111 and is welded at the penetrating portion to communicate the positive electrode chamber 18 and the sulfur container 30, the inlet is disposed at the upper part of the positive electrode chamber 18, and the outlet is at the upper part of the sulfur container 30. It is arranged.
- An upper lid 151 made of ⁇ -alumina is integrally bonded and fixed to the upper end surface of the cylindrical 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 cylindrical 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 cylindrical 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 cylindrical body 15 with a glass adhesive or the like.
- the sodium container 13 is disposed on the upper lid 151.
- a through hole is formed in the bottom of the sodium 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. become.
- an urging member 17 made of a carbon fiber mat is stored in the protective can 11 in a state compressed in the thickness direction.
- a current collector 20 made of a carbon fiber aggregate impregnated with molten sulfur 16 is inserted into the positive electrode chamber 18 formed in the cylindrical body 15. Further, a metal recovery pipe 110 is located at the center of the current collector 20 and functions as an anode.
- a metal bottom lid 111 is joined to the lower end surface of the cylindrical body 15 with a glass adhesive.
- the positive electrode chamber 18 is formed as a sealed 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.
- a negative electrode terminal 22 is joined to the sodium container 13, and an upper portion thereof protrudes upward through a through hole of the protective can 11.
- a positive electrode terminal 23 is joined to the upper side of the protective can 11.
- the molten sodium 14 in the negative electrode chamber 19 becomes sodium ions, passes through the portion of the cylindrical body 15 that forms the solid electrolyte partition, moves to the positive electrode chamber 18, and contacts with the molten sulfur 16. And discharge to produce sodium sulfide.
- the same amount of molten sodium 14 moved from the negative electrode chamber 19 to the positive electrode chamber 18 by discharge is replenished from the molten sodium 14 stored in the sodium container 13. Therefore, at the time of discharge, the molten sodium 14 in the sodium container 13 decreases, and the sodium sulfide in the positive electrode chamber 18 increases.
- sodium sulfide in the positive electrode chamber 18 is decomposed into sodium ions and molten sulfur 16, and the sodium ions permeate the solid electrolyte partition walls of the cylindrical body 15 and move to the negative electrode chamber 19 to melt.
- Sodium 14 is produced and returned to the sodium container 13.
- the molten sulfur 16 or sodium sulfide sucked up from the inlet of the first supply pipe unit 101 by the pump 120 from the sulfur container 30 passes through the supply pipe 100 to 2 is sent from the outlet of the supply pipe section 102 to the positive electrode chamber 18.
- the molten sulfur 16 or sodium sulfide filled in the positive electrode chamber 18 moves from the inlet of the recovery pipe 110 via the recovery pipe 110 to the sulfur container 30 from the outlet of the recovery pipe 110.
- the molten sulfur 16 is sent from the sulfur container 30 to the positive electrode chamber 18 and used for reaction with sodium ions.
- the generated sodium sulfide moves to the sulfur container 30.
- sodium sulfide is sent from the sulfur container 30 to the positive electrode chamber 18 and decomposes into molten sulfur 16.
- the generated molten sulfur 16 moves to the sulfur container 30.
- the control device 130 controls the operating state of the pump according to the charge / discharge reaction of the battery, and adjusts the amount and speed of movement of the molten sulfur 16 or sodium sulfide. As described above, in this embodiment, a large output can be obtained while securing a large battery capacity, and the battery performance can be improved.
- the shape of the cylindrical body made of the solid electrolyte used in Example 3 is not limited to the above-described one.
- the second cylindrical body having three positive electrode chambers 28 as shown in FIG. 25 can also be used.
- FIG. 5 is a cross-sectional view of a sodium-sulfur battery using the second cylindrical body 25.
- the second cylindrical body 25 has a columnar shape in which the outer peripheral shape extends in a circular axial direction.
- the second cylindrical 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 second cylindrical body 25 and the inner peripheral surface of the protective can 11. .
- three positive electrode chambers 28 parallel to the axial direction are formed in the second cylindrical body 25.
- the 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 second cylindrical body 25 By forming the second cylindrical body 25 in such a shape, the number of the positive electrode chambers 28 is increased, and an area where the positive electrode chambers 28 and the negative electrode chambers 29 are in contact with each other with a gap therebetween is further increased. That is, the area which becomes the partition wall of the solid electrolyte can be widened, and more sodium ions per unit time can permeate and react with the electrolyte, thereby improving the output of the battery. On the other hand, since the second cylindrical body 25 is formed in such a shape, the amount of the molten sulfur 16 stored in the positive electrode chamber 28 is reduced.
- FIG. 3 is a cross-sectional view of a sodium sulfur battery using the third cylindrical body 35. Similar to the cylindrical body 15, the third cylindrical body 35 has a columnar shape whose outer peripheral shape extends in the circular axial direction.
- the third cylindrical body 35 is housed in a metal cylindrical protective can 11, and the urging member 17 is disposed between the outer peripheral surface of the third cylindrical body 35 and the inner peripheral surface of the protective can 11. .
- seven positive electrode chambers 38 parallel to the axial direction are formed in the third cylindrical body 35.
- the 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.
- FIG. 7 is a cross-sectional view of a sodium sulfur battery using the fourth cylindrical body 65.
- the fourth cylindrical body 65 has a columnar shape with an outer peripheral shape extending in a quadrangular axial direction.
- the fourth cylindrical body 65 is accommodated in a metal cylindrical protective can 61 having a rectangular outer peripheral shape, and is attached between the outer peripheral surface of the fourth cylindrical body 65 and the inner peripheral surface of the protective can 61.
- a biasing member 67 is arranged inside the fourth cylindrical body 65.
- four positive electrode chambers 68 parallel to the axial direction are formed at the same shape position as the fourth cylindrical body 65.
- 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.
- the positive electrode chamber 68 and the negative electrode chamber 69 can be effectively formed in fixed space. Accordingly, in this case as well, the present invention is more suitably used, and a high output battery can be realized without reducing the battery capacity.
- the longitudinal cross-sectional view of the sodium sulfur battery 2 of Example 4 of this invention is shown in FIG.
- the sodium-sulfur battery 2 includes a metal bottomed cylindrical positive electrode container 41, a bottomed cylindrical solid electrolyte pipe 44 made of ⁇ -alumina disposed inside the positive electrode container 41, and a solid electrolyte pipe 44.
- a bottomed cylindrical negative electrode container 43 provided with a small hole 42 at the bottom thereof, a metal substantially bottomed cylindrical sodium container 57 disposed at the upper end of the positive electrode container 41,
- the main components are a pump 220 that supplies molten sulfur via the control device and a control device 230 that is connected to the pump 220 and controls the driving of the pump 220.
- the molten sulfur 16 is accommodated in the positive electrode chamber 48 which is divided by the inner peripheral surface side of the positive electrode container 41 and the outer peripheral surface side of the solid electrolyte tube 44 and is formed as a sealed space as described below.
- Molten sodium 14 is stored in the negative electrode container 43, and the molten sodium 14 is stored in a sodium container 57 positioned above the negative electrode container 43. A part of the molten sulfur 16 is stored in the sulfur container 31.
- the supply pipe 200 includes a first supply pipe part 201 that connects the sulfur container 31 and the pump 220, and a second supply pipe part 202 that connects the pump 220 and the positive electrode chamber 48.
- the first supply pipe portion 201 has an inlet disposed at a lower portion of the sulfur container 31, penetrates the side surface of the sulfur container 31, is welded at the penetrated portion, and communicates with the pump 220 at the tip.
- the second supply pipe portion 202 has an outlet disposed at the lower portion of the positive electrode chamber 48, penetrates the bottom portion of the positive electrode container 42, is welded at the penetrated portion, and further penetrates the side surface of the sulfur container 31 to penetrate therethrough.
- the welded portion is welded and communicated with the pump 220 at the tip.
- the recovery pipe 210 penetrates the bottom of the positive electrode container 41, is welded at the penetrating portion, communicates the positive electrode chamber 48 and the sulfur container 31, has an inlet disposed at the top of the positive electrode chamber 48, and has an outlet at the sulfur container 31. Arranged at the top.
- the positive electrode container 41 and the solid electrolyte tube 44 are coupled via a first insulating ring 46 and a positive electrode fitting 50. Thereby, the positive electrode chamber 48 becomes a sealed space.
- a negative electrode fitting 51 is joined to the upper end surface of the first insulating ring 46, and a negative electrode lid 52 is fixed to the negative electrode fitting 51 by welding.
- a sodium container 57 is joined to the upper end surface of the negative electrode lid 52, and the metal communication pipe 60 is welded through the upper end surface of the negative electrode lid 52 and the negative electrode container 43 from the bottom of the sodium container 57 and welded therethrough. Is provided.
- the metal communication pipe 60 communicates the sodium container 57 and the negative electrode container 43, and the molten sodium 14 moves inside.
- the sodium container 57 and the positive electrode container 41 are coupled via a second insulating ring 47.
- a positive electrode terminal 53 and a negative electrode terminal 54 are provided on the upper outer peripheral side surface of the positive electrode container 41 and the upper surface of the sodium container 57, respectively.
- a bottomed cylindrical safety tube 56 is provided outside the negative electrode container 43 and inside the solid electrolyte tube 44.
- the molten sodium 14 in the negative electrode container 43 is supplied into the safety tube 56 through the small holes 42, the safety tube 56 is filled with the supplied molten sodium 14, and the solid electrolyte tube 44. And the safety tube 56 is supplied into a negative electrode chamber 49.
- the molten sodium 14 in the negative electrode chamber 49 becomes sodium ions, passes through the solid electrolyte tube 44, moves into the positive electrode chamber 48, contacts with the molten sulfur 16, and discharges to generate sodium sulfide.
- the reduced amount of molten sodium 14 that has been used for the reaction in the negative electrode chamber 49 is replenished from the sodium container 57 through the metal communication pipe 60 and further used for the reaction.
- sodium sulfide in the positive electrode chamber 48 is decomposed into sodium ions and molten sulfur 16, and the sodium ions pass through the solid electrolyte tube 44 and move into the negative electrode chamber 49 to generate molten sodium 14.
- the container 43 and the sodium container 57 are returned.
- the molten sulfur 16 or sodium sulfide sucked up from the inlet of the first supply pipe unit 201 by the pump 220 from the sulfur container 31 passes through the supply pipe 200 to the first. 2 It is sent from the outlet of the supply pipe section 202 to the positive electrode chamber 48.
- the molten sulfur 16 or sodium sulfide filled in the positive electrode chamber 48 moves from the inlet of the recovery pipe 210 through the recovery pipe 210 to the sulfur container 31 from the outlet of the recovery pipe 210.
- the control device 230 controls the operating state of the pump according to the charge / discharge reaction of the battery, and adjusts the amount and speed of movement of the molten sulfur 16 or sodium sulfide. Therefore, in this embodiment, a large output can be obtained while securing a large battery capacity, and the battery performance can be improved.
- FIG. 9 shows a longitudinal sectional view of a sodium-sulfur battery 3 according to Embodiment 5 of the present invention
- FIG. 10 shows a side sectional view of an essential part of the sodium-sulfur battery 3.
- This sodium-sulfur battery 3 is provided separately from a metal box-shaped protective can 71, a plate-like body 75 made of ⁇ -alumina held in the space of the protective can 71, and the protective can 71.
- the sodium container 73, the metal communication pipe 74 that communicates the sodium container 73 and the protective can 71, the sulfur container 32 that is provided separately from the protective can 71, and the sulfur container 32 and the protective can 71 communicate with each other.
- the control device 330 is a main component.
- the plate-like body 75 has a plurality of independent fine pore-shaped negative electrode chambers 79 spaced apart from the center in the thickness direction of the plate-like upper end surface.
- the positive electrode chamber 78 is formed as a sealed space as described below, and the molten sulfur 16 is accommodated in the chamber.
- the supply pipe 300 includes a first supply pipe section 301 that connects the sulfur container 32 and the pump 320, and a second supply pipe section 302 that connects the pump 320 and the positive electrode chamber.
- the first supply pipe section 301 has an inlet disposed at the lower portion of the sulfur container 32, penetrates the side surface of the sulfur container 32, is welded at the penetrated portion, and communicates with the pump 320 at the tip.
- the second supply pipe section 302 has an outlet disposed in the lower portion of the positive electrode chamber 78, penetrates the bottom of the protective can 71, is welded at the penetrating portion, and further penetrates the side surface of the protective can 71 to penetrate therethrough.
- the welded portion is welded and communicated with the pump 320 at the tip.
- the recovery pipe 310 penetrates the bottom of the protective can 71, is welded at the penetrated portion, communicates the positive electrode chamber 78 and the sulfur container 32, has an inlet disposed at the upper part of the positive electrode chamber 78, and has an outlet at the sulfur container 32. Arranged at the top.
- An upper lid 351 made of ⁇ -alumina is integrally bonded and fixed to the upper end surface of the plate-like body 75 with a glass adhesive or the like, and a passage 72 that connects the pore-shaped negative electrode chamber 79 is formed.
- a sodium container 73 is disposed separately on the top of the upper lid 351.
- the metal communication pipe 74 penetrates the lower end surface of the sodium container 73 and the upper end surface of the upper lid 351, and is welded at the penetrated portion. Molten sodium 14 is held in the sodium container 73, and the molten sodium 14 passes through the communication pipe 74 and the passage 72 and flows into all the negative electrode chambers 79 to fill the negative electrode chambers 79.
- a current collector 80 made of a carbon fiber aggregate impregnated with sulfur 16 is inserted into the positive electrode chamber 78 formed on the outer periphery of the plate-like body 75.
- the upper end of the protective can 71 is joined to the upper end of the plate-like body 75, whereby the positive electrode chamber 78 becomes a sealed space.
- a negative electrode terminal 81 is bonded to the upper end surface of the sodium container 73, and a positive electrode terminal 82 is bonded to the upper outer peripheral side surface of the protective can 71.
- the molten sodium 14 in the negative electrode chamber 78 becomes sodium ions and passes through the portion of the plate-like body 75 that forms the partition wall of the solid electrolyte, moves to the positive electrode chamber 78, and contacts with the molten sulfur 16. And discharge to produce sodium sulfide.
- the same amount of molten sodium 14 moved from the negative electrode chamber 79 to the positive electrode chamber 78 by discharge is replenished from the molten sodium 14 stored in the sodium container 73.
- the sodium sulfide in the positive electrode chamber 78 is decomposed to become sodium ions and molten sulfur 16, and the sodium ions pass through the portion of the plate-like body 75 serving as the partition walls of the solid electrolyte and move to the negative electrode chamber 79 to be melted.
- Sodium 14 is produced and returned to the sodium container 73.
- the molten sulfur 16 or sodium sulfide sucked up from the inlet of the first supply pipe section 301 by the pump 320 from the sulfur container 32 passes through the supply pipe 300 to 2 It is sent to the positive electrode chamber 78 from the outlet of the supply pipe section 302.
- the molten sulfur 16 or sodium sulfide filled in the positive electrode chamber 78 moves from the inlet of the recovery pipe 310 via the recovery pipe 310 to the sulfur container 32 from the outlet of the recovery pipe 310.
- the control device 330 controls the operating state of the pump in accordance with the charge / discharge reaction of the battery, and adjusts the amount and speed of movement of the molten sulfur 16 or sodium sulfide.
- most of the molten sodium 14 and molten sulfur 16 used for the battery reaction are stored in the sodium container 73 and the sulfur container 32, respectively, so that the battery reaction is actually performed.
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Abstract
Description
前記正極室から前記正極活物質容器へ、さらに前記正極活物質容器から前記正極室へ前記正極活物質を一方向に循環移動させる通路手段とを備えたことを特徴とする。
本発明は、負極室と連通し負極活物質を送受する負極活物質容器を備えるものとするのが好ましい。負極活物質の大部分をこの負極活物質容器に収納し、容器形状体の負極室内に収納されている負極活物質の量を少なくするのが好ましい。負極活物質容器を用いることにより、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、負極活物質容器に多量の負極活物質を収納することもできるため、電池容量を大きくすることができる。
以下、本発明の二次電池の実施例を挙げて本発明をさらに具体的に説明する。
そして、正極容器11の内周面側と固体電解質間15の外周面側によって区画され、下記するように密閉空間として形成される正極室18内に溶融硫黄16が収納され、負極容器13内に溶融ナトリウム14が収納される。また、補助容器10と正極容器11の底部によって密閉空間として形成される補助室17内には溶融硫黄16が一部収納されている。
供給管20は、正極容器11の底部を貫通し、その貫通した部分で溶接され正極室18と補助室17を連通し、一方の端部は補助室17の下部に配設され、他方の端部は、正極室18の下部に配設されている。そして、図3に示すように、供給管20の内部に、溶融硫黄16が補助室17の下部から正極室18の下部へ流れる方向を一方方向とする逆止弁201が設けられ、補助室17の下部と正極室18の下部はそれぞれ供給管20の入口と出口となる。
回収管21は、正極容器11の底部を貫通し、その貫通した部分で溶接され正極室18と補助室17を連通し、一方の端部は正極室18の上部に配設され、他方の端部は、補助室17の上部に配設されている。そして、回収管21の内部に、溶融硫黄16が正極室18の上部から補助室17の下部へ流れる方向を一方方向とする逆止弁211が設けられ、正極室18の上部と補助室17の上部はそれぞれ回収管21の入口と出口となる。なお、逆止弁211は、図3で示すものと同様のものである。
正極容器11と固体電解質管15とは、絶縁リング22及び正極金具23を介して結合されている。これにより、正極室18は密閉空間となる。また絶縁リング22の上端面には負極金具24が接合され、この負極金具24に負極蓋25が溶接固定されている。正極容器11の外周上部と負極蓋25の上面には、それぞれ正極端子26と負極端子27が設けられている。また、負極容器13の外側で、固体電解質管15の内側に、有底筒状の安全管28が備えられている。
このナトリウム硫黄電池1は、放電時には、負極容器13内の溶融ナトリウム14が小孔12を通じて安全管28内に供給され、供給された溶融ナトリウム14により安全管28が満たされ、さらに固体電解質管15と安全管28との間に形成される負極室19内に供給される。そして負極室19内の溶融ナトリウム14がナトリウムイオンとなり、固体電解質管15を透過して正極室18内に移動し、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。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固体電解質管15を透過して負極室19内に移動して溶融ナトリウム14を生成し、負極容器13に戻される。
このように、放電時には、イオン化された溶融ナトリウム14が負極室19から正極室18へ移動して、正極室18内には硫化ナトリウムの量が増加するため、正極室18内の液面が次第に上昇する。従って、密閉空間である正極室18内の圧力が徐々に高くなる。そのため、補助室17側の圧力よりも正極室18側の圧力が高くなり、その圧力差によって回収管21内の逆止弁211が開かれる。その後、回収管21を通って、溶融硫黄16が正極室18から補助室17へ移動する。このとき、供給管20内の逆止弁201は、溶融硫黄16が正極室18から補助室17へ流れる方向には開かないため、供給管20を通って、溶融硫黄16が移動することはない。
一方、充電時には、イオン化された溶融ナトリウム14が正極室18から負極室19へ移動するため、正極室18内には多硫化ナトリウムの量が減少して、正極室18内の液面が次第に下がる。従って、密閉空間である正極室18内の圧力が徐々に低くなる。また、放電時の反応により、正極室18から移動した溶融硫黄16により補助室17内の液面が上昇しているから、同じく密閉空間である補助室17内の圧力は高くなっている。そのため、正極室18側の圧力よりも補助室17側の圧力が高くなり、その圧力差によって供給管20内の逆止弁201が開かれる。その後、供給管20を通って、溶融硫黄16が補助室17から正極室18へ移動する。このとき、回収管21内の逆止弁211は、溶融硫黄16が補助室17から正極室18へ流れる方向には開かないため、回収管21を通って、溶融硫黄16が移動することはない。
このように溶融硫黄16が循環移動するので、多硫化ナトリウムが正極室18の下部に集中して溜まる現象を抑えることができる。また、溶融硫黄16は、一方方向に循環移動するため、正極室18内の溶融硫黄16の濃度をほぼ均一に保つことができる。従って、活物質を効率的に利用することが可能となり、電池性能を向上させることができる。
そして、筒状体35は肉厚の筒状で、軸孔に当たる内部空間が正極室18となる。この筒状体35の内周面に沿い僅かな間隙を隔てて軸方向に延びる細孔状の負極室49が周方向に間隔を隔て多数形成されている。正極室48は、下記するように密閉空間として形成され室内には溶融硫黄16が収納される。また、ナトリウム容器33内には溶融ナトリウム14が収納され、補助容器30と保護缶31の底部である底蓋311によって密閉空間として形成される正極室18内には溶融硫黄16が一部収納されている。
供給管40は、底蓋311を貫通し、その貫通した部分で溶接され正極室18と補助容器30内を連通し、一方の端部は補助容器30内の下部に配設され、他方の端部は、正極室18の下部に配設されている。そして、供給管40の内部に、溶融硫黄16が補助容器30内の下部から正極室48の下部へ流れる方向を一方方向とする逆止弁401が設けられ、補助容器30内の下部と正極室18の下部はそれぞれ供給管40の入口と出口となる。
回収管41は、底蓋311を貫通し、その貫通した部分で溶接され正極室18と補助容器30内とを連通し、一方の端部は正極室18の上部に配設され、他方の端部は、補助容器30内の上部に配設されている。そして、回収管41の内部に、溶融硫黄16が正極室18の上部から補助容器30内の下部へ流れる方向を一方方向とする逆止弁411が設けられ、正極室18の上部と補助容器30内の上部はそれぞれ回収管41の入口と出口となる。
筒状体35の上端面には、αアルミナで形成される上蓋351がガラス接着材等で一体的に接合固定される。この上蓋351は、その下面にリング状の溝を持ち、この溝の開口面が筒状体35の上端面で閉じられてリング状通路352となる。このリング状通路352には、筒状体35の全ての負極室49の上端開口と連通する。この上蓋351の上面からリング状通路352に延びる垂直通路353をもつ。筒状体35の下端面には、αアルミナで形成された封止リング355がガラス接着材等で一体的に接合固定される。
上蓋351の上にナトリウム容器33が配置される。ナトリウム容器33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353とに、軸孔を持つ金属製の接続管354が挿着接合される。ナトリウム容器33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354の軸孔、垂直通路353、リング状通路352を通り、全ての負極室49に流入し、負極室49を満たすことになる。
また、筒状体35の外周面と保護缶31の内周面との間には、炭素繊維マットからなる付勢部材37が厚さ方向に圧縮された状態で、保護缶31に納められる。
筒状体35に形成された正極室18には溶融硫黄16が含浸された炭素繊維集積体からなる集電体38が挿着される。さらにこの集電体38中心部分に金属製の回収管41が位置し、陽極として働く。
正極室18の底には、金属製の底蓋311が筒状体35の下端面にガラス接着材で接合される。以上により正極室18は密閉空間として形成される。
なお、底蓋311は保護缶31の側周部に溶接され保護缶31の底部分となる。また、ナトリウム容器33には負極端子37が接合され、その上側部分は保護缶31の通し穴を通って上方に突出している。さらに保護缶31の上側には正極端子36が接合されている。
このナトリウム硫黄電池2は、放電時に負極室49内の溶融ナトリウム14がナトリウムイオンとなり筒状体35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49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容器33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筒状体35の固体電解質の隔壁となる部分を透過して負極室49に移動して溶融ナトリウム14を生成し、ナトリウム容器33内に戻る。
実施例1と同様に、充放電時の正極室18と補助容器30内の圧力差により、回収管41及び供給管40を通って、溶融硫黄16が正極室18内と補助容器30内を循環移動する。このような溶融硫黄16の循環移動によって、多硫化ナトリウムが正極室18の下部に集中して溜まる現象を抑えることができる。また、溶融硫黄16は、一方方向に循環移動するため、正極室18内の溶融硫黄16の濃度をほぼ均一に保つことができる。従って、活物質を効率的に利用することが可能となり、電池性能を向上させることができる。
そして、筒状体15は肉厚の筒状で、軸孔に当たる内部空間が正極室18となる。この筒状体15の内周面に沿い僅かな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。正極室18は、下記するように密閉空間として形成され室内には溶融硫黄16が収納される。また、ナトリウム容器13内には溶融ナトリウム14が収納され、硫黄容器30内には溶融硫黄16が一部収納されている。
供給管100は、硫黄容器16とポンプ120を繋ぐ第1供給管部101と、ポンプ120と正極室18を繋ぐ第2供給管部102とから構成される。第1供給管部101は、入口が硫黄容器30の下部に配設され、保護缶11の側面を貫通し、その貫通した部分で溶接されその先でポンプ120と連通される。第2供給管部102は、出口が正極室18の下部に配設され、底蓋111を貫通し、その貫通した部分で溶接され、さらに、保護缶11の側面を貫通し、その貫通した部分で溶接されその先でポンプ120と連通される。
回収管110は、底蓋111を貫通し、その貫通した部分で溶接され正極室18と硫黄容器30を連通し、入口が正極室18の上部に配設され、出口が硫黄容器30の上部に配設されている。筒状体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、この溝の開口面が筒状体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、筒状体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。
筒状体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。上蓋151の上にナトリウム容器13が配置される。ナトリウム容器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、筒状体15の外周面と保護缶11の内周面との間には、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。
筒状体15に形成された正極室18には溶融硫黄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回収管110が位置し、陽極として働く。
正極室18の底には、金属製の底蓋111が筒状体15の下端面にガラス接着材で接合される。以上により正極室18は密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。また、ナトリウム容器13には負極端子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の上側には正極端子23が接合されている。
このナトリウム硫黄電池1は、放電時に負極室19内の溶融ナトリウム14がナトリウムイオンとなり筒状体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筒状体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、ナトリウム容器13内に戻る。
本実施例では、以上のような充放電反応時において、硫黄容器30からポンプ120によって第1供給管部101の入口から吸い上げられた溶融硫黄16又は硫化ナトリウムは供給管100を経由して、第2供給管部102の出口から正極室18に送られる。そして、正極室18内に充満した溶融硫黄16又は硫化ナトリウムは、回収管110の入口から回収管110を経由して、回収管110の出口から硫黄容器30に移動する。
放電時では、硫黄容器30から溶融硫黄16が正極室18に送られ、ナトリウムイオンとの反応に供される。一方、生成された硫化ナトリウムは硫黄容器30に移動する。充電時には、硫黄容器30から硫化ナトリウムが正極室18に送られ、分解して溶融硫黄16となる。一方、生成された溶融硫黄16は硫黄容器30に移動する。
制御装置130は、電池の充放電反応に応じて、ポンプの稼動状態を制御し、溶融硫黄16又は硫化ナトリウムが移動する量や速度を調節する。
以上のように本実施例では、大きな電池容量を確保しつつ大きな出力が得られ、電池性能を向上させることができる。
なお、実施例3で用いられる固体電解質からなる筒状体の形状は、上記したものに限られるものではなく、例えば、図5に示すような3個の正極室28を有する第2筒状体25を用いることもできる。なお、図5はこの第2筒状体25を用いたナトリウム硫黄電池の横断面図である。
第2筒状体25は、筒状体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。第2筒状体25は、金属製の筒状の保護缶11に収納され、第2筒状体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。
第2筒状体25の内部には、図5に示すように、軸方向に平行する3個の正極室28が形成されている。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個の正極室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。
第2筒状体25をこのような形状とすることで、正極室28の数が増え、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、単位時間当たり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電池の出力が向上する。一方、第2筒状体25をこのような形状にしたことで、正極室28に収納される溶融硫黄16の量は減ることになる。しかし、本発明は、硫黄容器30内に多量の溶融硫黄16を収納しておくことができるため、ポンプ120を駆動させることにより供給管100を介してそれぞれの正極室28内に溶融硫黄16を連続的に供給することができるから、電池容量を低下させることなく、高出力の電池を実現することができる。
さらに、図6に示すような7個の正極室38を有する第3筒状体35を用いることができる。なお、図3はこの第3筒状体35を用いたナトリウム硫黄電池の横断面図である。
第3筒状体35は、筒状体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。第3筒状体35は、金属製の筒状の保護缶11に収納され、第3筒状体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。
第3筒状体35の内部には、図6に示すように、軸方向に平行する7個の正極室38が形成されている。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個の正極室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。
第3筒状体35をこのような形状とすることで、正極室38に収納される溶融硫黄16の量はさらに減ることになるが、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。従って、この場合には、本発明はより好適に用いられ、電池容量を低下させることなく、高出力の電池を実現することができる。
さらに、図7に示すような4個の正極室68を有する第4筒状体65を用いることができる。なお、図7はこの第4筒状体65を用いたナトリウム硫黄電池の横断面図である。
第4筒状体65は、図7に示すように、外周形状が四角形の軸方向に延びる柱形状である。第4筒状体65は、外周形状が四角形状である金属製の筒状の保護缶61に収納され、第4筒状体65の外周面と保護缶61の内周面との間に付勢部材67が配置される。
第4筒状体65の内部には、軸方向に平行する4個の正極室68が第4筒状体65と同じ形状位置で形成されている。正極室68は、断面四角形状の軸方向に延びる孔状である。そして、4個の正極室68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69が一定の間隔で連続的に形成されている。負極室69は、断面矩形状の軸方向に延びる孔状である。
第4筒状体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。
従って、この場合にも、本発明はより好適に用いられ、電池容量を低下させることなく高出力の電池を実現することができる。
そして、正極容器41の内周面側と固体電解質管44の外周面側によって区画され、下記するように密閉空間として形成される正極室48内に溶融硫黄16が収納されている。負極容器43内には溶融ナトリウム14が収納され、さらに負極容器43の上部に位置するナトリウム容器57に溶融ナトリウム14が収納されている。また、硫黄容器31内には溶融硫黄16が一部収納されている。
供給管200は、硫黄容器31とポンプ220を繋ぐ第1供給管部201と、ポンプ220と正極室48を繋ぐ第2供給管部202とから構成される。第1供給管部201は、入口が硫黄容器31の下部に配設され、硫黄容器31の側面を貫通し、その貫通した部分で溶接されその先でポンプ220と連通される。第2供給管部202は、出口が正極室48の下部に配設され、正極容器42の底部を貫通し、その貫通した部分で溶接され、さらに、硫黄容器31の側面を貫通し、その貫通した部分で溶接されその先でポンプ220と連通される。
回収管210は、正極容器41の底部を貫通し、その貫通した部分で溶接され正極室48と硫黄容器31を連通し、入口が正極室48の上部に配設され、出口が硫黄容器31の上部に配設されている。正極容器41と固体電解質管44とは、第1絶縁リング46及び正極金具50を介して結合されている。これにより、正極室48は密閉空間となる。また第1絶縁リング46の上端面には負極金具51が接合され、この負極金具51に負極蓋52が溶接固定されている。さらに負極蓋52の上端面にはナトリウム容器57が接合され、ナトリウム容器57の底部から負極蓋52及び負極容器43の上端面を貫通してその貫通した部分で溶接される金属製の連通管60が設けられている。金属製の連通管60はナトリウム容器57と負極容器43を連通し、内部を溶融ナトリウム14が移動する。ナトリウム容器57と正極容器41とは、第2絶縁リング47を介して結合されている。
正極容器41の上部外周側面とナトリウム容器57の上面には、それぞれ正極端子53と負極端子54が設けられている。また、負極容器43の外側で、固体電解質管44の内側に、有底筒状の安全管56が備えられている。
このナトリウム硫黄電池2は、放電時には、負極容器43内の溶融ナトリウム14が小孔42を通じて安全管56内に供給され、供給された溶融ナトリウム14により安全管56が満たされ、さらに固体電解質管44と安全管56との間に形成される負極室49内に供給される。そして負極室49内の溶融ナトリウム14がナトリウムイオンとなり、固体電解質管44を透過して正極室48内に移動し、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。そして、負極室49内の反応に供され減少した分の溶融ナトリウム14は、金属製の連通管60を通じてナトリウム容器57から補充され、さらに反応に供される。充電時には、正極室48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固体電解質管44を透過して負極室49内に移動して溶融ナトリウム14を生成し、負極容器43及びナトリウム容器57に戻される。
本実施例では、以上のような充放電反応時において、硫黄容器31からポンプ220によって第1供給管部201の入口から吸い上げられた溶融硫黄16又は硫化ナトリウムは供給管200を経由して、第2供給管部202の出口から正極室48に送られる。そして、正極室48内に充満した溶融硫黄16又は硫化ナトリウムは、回収管210の入口から回収管210を経由して、回収管210の出口から硫黄容器31に移動する。
また、制御装置230は、電池の充放電反応に応じて、ポンプの稼動状態を制御し、溶融硫黄16又は硫化ナトリウムが移動する量や速度を調節する。従って、本実施例では、大きな電池容量を確保しつつ大きな出力が得られ、電池性能を向上させることができる。
このナトリウム硫黄電池3は、金属製の箱状の保護缶71と、保護缶71の空間内に保持されたβアルミナから作られる板状体75と、保護缶71と分離独立して設けられたナトリウム容器73と、ナトリウム容器73と保護缶71とを連通する金属製の連通管74と、保護缶71と分離独立して設けられた硫黄容器32と、硫黄容器32と保護缶71とを連通する金属製の供給管300及び回収管310と、硫黄容器32の外側に配設され供給管300を介して溶融硫黄16を供給するポンプ320と、ポンプ320に接続されポンプ320の駆動を制御する制御装置330と、を主な構成部分としている。
そして、保護缶71の内周面側と板状体75の外周面側により形成される内部空間が正極室78となる。この板状体75は、板状の上端面の厚さ方向の中央から下方に複数の独立した細孔状の負極室79が間隔を隔て形成されている。正極室78は、下記するように密閉空間として形成され室内には溶融硫黄16が収納される。また、ナトリウム容器73内には溶融ナトリウム14が収納され、硫黄容器32内には溶融硫黄16が一部収納されている。
供給管300は、硫黄容器32とポンプ320を繋ぐ第1供給管部301と、ポンプ320と正極室を繋ぐ第2供給管部302とから構成される。第1供給管部301は、入口が硫黄容器32の下部に配設され、硫黄容器32の側面を貫通し、その貫通した部分で溶接されその先でポンプ320と連通される。第2供給管部302は、出口が正極室78の下部に配設され、保護缶71の底部を貫通し、その貫通した部分で溶接され、さらに、保護缶71の側面を貫通し、その貫通した部分で溶接されその先でポンプ320と連通される。
回収管310は、保護缶71の底部を貫通し、その貫通した部分で溶接され正極室78と硫黄容器32を連通し、入口が正極室78の上部に配設され、出口が硫黄容器32の上部に配設されている。
板状体75の上端面には、αアルミナで形成される上蓋351がガラス接着材等で一体的に接合固定され、細孔状の負極室79を結ぶ通路72が形成されている。上蓋351の上部には、分離してナトリウム容器73が配置される。金属製の連通管74は、ナトリウム容器73の下端面と上蓋351の上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。ナトリウム容器73には溶融ナトリウム14が保持され、溶融ナトリウム14は、連通管74、通路72を通り、全ての負極室79に流入し、負極室79を満たすことになる。
板状体75の外周に形成された正極室78には硫黄16が含浸された炭素繊維集積体からなる集電体80が挿着される。
保護缶71の上端は、板状体75の上端と接合され、これにより正極室78は密閉空間となる。
なお、ナトリウム容器73の上端面には負極端子81が接合され、さらに保護缶71の上部外周側面には正極端子82が接合されている。
このナトリウム硫黄電池3は、放電時に負極室78内の溶融ナトリウム14がナトリウムイオンとなり板状体75の固体電解質の隔壁となる部分を透過して正極室78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79から正極室78に移動した同じ量の溶融ナトリウム14はナトリウム容器73に収納されている溶融ナトリウム14から補充される。
充電時には、正極室78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板状体75の固体電解質の隔壁となる部分を透過して負極室79に移動して溶融ナトリウム14を生成し、ナトリウム容器73内に戻る。
本実施例では、以上のような充放電反応時において、硫黄容器32からポンプ320によって第1供給管部301の入口から吸い上げられた溶融硫黄16又は硫化ナトリウムは供給管300を経由して、第2供給管部302の出口から正極室78に送られる。そして、正極室78内に充満した溶融硫黄16又は硫化ナトリウムは、回収管310の入口から回収管310を経由して、回収管310の出口から硫黄容器32に移動する。
また、制御装置330は、電池の充放電反応に応じて、ポンプの稼動状態を制御し、溶融硫黄16又は硫化ナトリウムが移動する量や速度を調節する。
また、本実施例のナトリウム硫黄電池3では、電池反応に供される溶融ナトリウム14及び溶融硫黄16の大部分は、それぞれナトリウム容器73及び硫黄容器32に収納され、実際に電池反応が行われる保護缶71の内部では、その都度、反応に供される溶融ナトリウム14と溶融硫黄16しか収納されていない。すなわち、活物質を収納するスペースと活物質が反応するスペースを分離独立して設けている。このように機能分化をすることによって、安全性の高いナトリウム硫黄電池を実現することができかつ、大きな電池容量を確保しつつ大きな出力が得られ、電池性能を向上させることができる。
Claims (15)
- 正極活物質が少なくとも収納された正極室と、負極活物質が少なくとも収納された負極室と、前記正極室と前記負極室の間に位置して前記正極活物質と前記負極活物質を隔離し、かつ前記負極活物質に対して伝導性を有する壁状の固体電解質とを備えた二次電池であって、
前記正極室と独立し前記正極活物質の少なくとも一部を収納する正極活物質容器と、前記正極室から前記正極活物質容器へ、さらに前記正極活物質容器から前記正極室へ前記正極活物質を一方向に循環移動させる通路手段とを備えたことを特徴とする固体電解質二次電池。 - 前記通路手段は、前記正極室から正極活物質容器へ前記正極活物質を移動させる第1一方向弁を有する第1通路と、前記正極活物質容器から前記正極室へ前記正極活物質を移動させる第2一方向弁を有する第2通路と、を備える請求項1記載の固体電解質二次電池。
- 前記第1通路と前記第2通路の一方の通路の入口は、前記正極室の上部に配設されかつ出口は前記正極活物質容器の上部に配設され、前記第1通路と前記第2通路の他方の通路の入口は、前記正極活物質容器の下部に配設されかつ出口は前記正極室の下部に配設される請求項1記載の固体電解質二次電池。
- 前記正極活物質は硫黄であり、前記負極活物質はナトリウムである請求項1記載の固体電解質二次電池。
- 前記通路手段を介して前記正極活物質を移動させる移動手段を備える請求項1記載の固体電解質二次電池。
- 前記通路手段は、前記正極室から前記正極活物質容器へ前記正極活物質を移動させる第1通路と、
前記正極活物質容器から前記正極室へ前記正極活物質を移動させる第2通路と、を備える請求項5記載の固体電解質二次電池。 - 前記第1通路と前記第2通路の一方の通路の入口は、前記正極室の上部に配設されかつ出口は前記正極活物質容器の上部に配設され、前記第1通路と前記第2通路の他方の通路の入口は、前記正極活物質容器の下部に配設されかつ出口は前記正極室の下部に配設される請求項5記載の固体電解質二次電池。
- 前記移動手段を制御する制御手段を備える請求項5記載の固体電解質二次電池。
- 前記移動手段はポンプである請求項5記載の固体電解質二次電池。
- 前記固体電解質は、少なくとも一個の前記正極室と、前記正極室の壁面に沿い前記壁面より間隔を隔て断面が前記正極室より小面積の複数個の前記負極室とをもつ容器形状体である請求項5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10記載の固体電解質二次電池。
- 前記容器形状体は、柱形状体である請求項10記載の固体電解質二次電池。
- 前記容器形状体の少なくとも一部の外側面に当接し、前記容器形状体を中心側に付勢する付勢部材をもつ請求項5記載の固体電解質二次電池。
- 前記負極室と連通し前記負極活物質を送受する負極活物質容器を備える請求項5記載の固体電解質二次電池。
- 前記正極活物質は硫黄であり、前記負極活物質はナトリウムである請求項5記載の固体電解質二次電池。
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KR101445208B1 (ko) | 2014-09-29 |
JPWO2011152028A1 (ja) | 2013-07-25 |
CN102906930B (zh) | 2016-09-14 |
KR20130040946A (ko) | 2013-04-24 |
CN102906930A (zh) | 2013-01-30 |
JP5869477B2 (ja) | 2016-02-24 |
EP2579380B1 (en) | 2017-04-26 |
US20130065098A1 (en) | 2013-03-14 |
EP2579380A1 (en) | 2013-04-10 |
EP2579380B9 (en) | 2017-09-06 |
US9300012B2 (en) | 2016-03-29 |
EP2579380A4 (en) | 2015-08-26 |
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