JP2012099293A - Sodium-sulfur battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sodium-sulfur battery having shock-resistant and high current density.SOLUTION: In a sodium-sulfur battery 1 using sodium 4, sulfur 11, and sodium sulfide 12 as an active material, the outer shape of an electrolyte 14 that separates the positive electrode from the negative electrode is rod-shaped or plate-shaped, one or more narrow rod-shaped sodium flow paths 13 or thin plate-shaped sodium flow paths 13 are provided around the center of the electrolyte 14, and the area size of the electrolyte 14 is increased by arranging the plurality of electrolytes 14 or arranging the electrolyte 14 in a honeycomb, thereby obtaining the high current density, and is vibration proof and impact resistance.

Description

Sodium sulfur battery.

A sodium-sulfur battery using sodium as a negative electrode active material and sulfur and sodium sulfide as a positive electrode active material uses a beta alumina solid electrolyte that permeates sodium ions to separate the positive electrode and the negative electrode.
The sodium-sulfur battery discharges when sodium in the negative electrode permeates the electrolyte, moves to the positive electrode, combines with sulfur and becomes sodium sulfide, discharges from the sodium sulfide of the positive electrode, permeates the electrolyte, and passes through the electrolyte to sodium into the negative electrode Moves and charges.
The structure of the sodium-sulfur battery is divided into a positive electrode chamber and a negative electrode chamber with an insulating partition wall and a bag tube or flat electrolyte joined to the partition wall, and a positive electrode can is joined to the partition wall to become a positive electrode chamber. Sodium is accommodated, a negative electrode can is joined to the partition wall, and the inside becomes a negative electrode chamber and contains sulfur and sodium sulfide.

JP 2003-068356 A JP 2005-149773 A

In order to employ a sodium-sulfur battery as a power source for automobiles and the like, charging / discharging in a short time is required, and current density is insufficient in conventional batteries. In addition, it is necessary to provide a highly safe battery that can withstand various vibrations over a long period of time and that will not be damaged by an impact caused by a collision.

In a sodium-sulfur battery using sodium as the negative electrode active material and sulfur and sodium sulfide as the positive electrode active material, the outer shape of the electrolyte separating the positive electrode and the negative electrode is made into a rod shape or plate shape, and single or multiple rod-like thin sodium at the center of the electrolyte A channel or a thin plate-like sodium channel is provided.
The plate-like electrolyte of a sodium-sulfur battery is bent, branched, or joined.
The inside of the sodium-sulfur battery is divided into a negative electrode chamber and a positive electrode chamber by a partition, and an arbitrary number of electrolytes are joined to the partition and held in the positive electrode chamber, and the negative electrode chamber and the sodium channel are connected by a plurality of holes formed in the partition. .

A porous support layer is provided on the negative electrode side of the electrolyte of the sodium sulfur battery.
A porous insulating layer is provided on the positive electrode side of the electrolyte of the sodium-sulfur battery, and a porous connection layer in which an insulating material and a conductive material are mixed is further provided thereon.
Materials with high toughness and high thermal conductivity are used for the support layer and connection layer of sodium-sulfur batteries.

All or part of the sodium flow path, the support layer, the electrolyte, the insulating layer, and the connection layer of the sodium-sulfur battery are formed at one time by extrusion, and sintered to be integrated.
The electrolyte of the sodium-sulfur battery and the partition walls are simultaneously sintered and integrated.
A positive electrode plate parallel to the electrolyte of the sodium sulfur battery is provided, and a number of gaps parallel to the direction of current flow are provided in the positive electrode plate.
A conductive negative electrode plate is provided in the negative electrode chamber of the sodium sulfur battery in parallel with the partition.

The negative electrode plate of the sodium sulfur battery is connected to the negative electrode can by a conductive column or plate, and the positive electrode plate is joined to the bottom of the positive electrode can.
The negative electrode plate of the sodium-sulfur battery is joined to the negative electrode can, the negative electrode that is insulated from the positive electrode can and extended to the end of the positive electrode can is joined to the outer surface of the negative electrode can, and the positive electrode plate is joined to the side surface of the positive electrode can.
The partition wall and the negative electrode can of the sodium-sulfur battery are L-shaped, the sodium flow path and the negative electrode chamber are connected by a hole formed in the side surface of the partition wall, and the positive electrode plate is joined to the side surface of the positive electrode can.

Use iron-based metal or iron-aluminum plywood for sodium-sulfur battery cans.
A metallized layer is formed on the end face of the partition wall of the sodium-sulfur battery, and the can and the metallized layer of the partition wall are welded.
After assembling the sodium-sulfur battery can, the inside of the positive electrode chamber is plated.
The outer shape of the sodium-sulfur battery is rectangular, and insulation is applied to the outer periphery other than the surface to be the battery electrode.

In a sodium-sulfur battery using sodium as the negative electrode active material and sulfur and sodium sulfide as the positive electrode active material, the outer shape of the electrolyte separating the positive electrode and the negative electrode is made into a rod shape or plate shape, and single or multiple rod-like thin sodium at the center of the electrolyte By providing a channel or a thin plate-like sodium channel, the volume per unit area of the electrolyte can be reduced. Therefore, even if the area of the electrolyte is increased to increase the current density of the battery, the volume of the electrolyte occupying the volume of the battery does not increase extremely, and the decrease in the electric capacity of the battery is reduced.
By bending, branching, or joining the plate-shaped electrolyte of a sodium-sulfur battery, it can be made into various shapes of electrolyte, and the electrolyte can withstand stress from multiple directions, increasing the impact resistance of the battery. be able to.

The interior of the sodium-sulfur battery is divided into a negative electrode chamber and a positive electrode chamber by a partition, an arbitrary number of electrolytes are joined to the partition and held in the positive electrode chamber, and the negative electrode chamber and the sodium channel are connected by a plurality of holes opened in the partition If the battery can be installed so that the upper part becomes the negative electrode chamber and the lower part becomes the positive electrode chamber, sodium is naturally supplied by gravity to the sodium flow path of the electrolyte held in the positive electrode chamber through the hole formed in the partition wall.
In addition, since the positive electrode chamber and the negative electrode chamber are separated by a partition wall, even if the electrolyte is severely damaged, the active material of the battery does not mix rapidly, and the battery can be prevented from being heated to a high temperature.
In addition, the electrolyte can have a complex shape or a plurality of electrolytes can be provided to increase the area of the electrolyte, and the current density of the battery can be increased in proportion to the area of the electrolyte. In addition, by arranging electrolytes in a shape that allows many electrolytes to be juxtaposed or intricately divided into sections, the volume of positive electrode active material applied to a single electrolyte is reduced, and vibrations and shocks received by the electrolyte are dispersed. Can do.

If a porous support layer is provided on the negative electrode side of the electrolyte of the sodium sulfur battery, the support layer receives the vapor pressure of sulfur applied to the electrolyte, and it is not necessary to withstand the vapor pressure alone, so the thickness of the electrolyte can be reduced. The resistance value of the electrolyte decreases and the current density of the battery can be increased.
When a porous insulating layer is provided on the positive electrode side of the electrolyte of a sodium-sulfur battery, and a porous connecting layer in which an insulating material and a conductive material are further mixed is provided thereon, the movement of sodium sulfide is connected to the connecting layer. Therefore, the insulating layer can be limited only to the insulating function, and the thickness of the insulating layer can be reduced.
In addition, the conductive material of the connection layer is also responsible for the movement of sulfur, and since the insulating layer is thin, the sulfur of the connection layer and the electrolyte approach each other and the diffusion distance of sodium ions is shortened. Further, the connection layer becomes a substantial positive electrode, and the resistance value between the insulating layer and the positive electrode plate is lowered by the conductive material of the connection layer. With these effects, the resistance value between the electrolyte and the positive electrode plate decreases, and the current density of the battery can be increased.

When a porous support layer is provided on the negative electrode side of the electrolyte of a sodium-sulfur battery, and a porous connection layer is provided on the positive electrode side of the electrolyte with a porous insulating layer sandwiched therebetween, the electrolyte becomes a support layer, an insulating layer, or a connection layer. Therefore, even if a crack occurs in the electrolyte, the electrolyte does not scatter and the crack does not spread. As a result, the volume of the positive electrode active material entering from the crack is limited, and the sodium sulfide having a high melting temperature generated by reaction with sodium is captured by the support layer, and the crack is eventually closed.
When a tough material is used for the support layer and connection layer of the sodium-sulfur battery, an electrolyte that is resistant to impact can be obtained even if it is thin by withstanding the impact in the support layer and connection layer. In addition, if a material with high thermal conductivity is used for the support layer and the connection layer, even if the current concentrates locally on the electrolyte at the end of discharge of the battery and heat is generated, the heat is dispersed and the battery can withstand high current density. can get.

All or part of the sodium flow path, support layer, electrolyte, insulating layer, and connection layer of a sodium-sulfur battery are formed at one time by extrusion, and sintered to form a single unit, resulting in a highly rigid electrolyte. Productivity is also improved.
If the electrolyte and partition walls of the sodium-sulfur battery are simultaneously sintered and integrated, it is possible to eliminate the trouble of assembling and joining the electrolyte and partition walls later.

When a positive electrode plate parallel to the electrolyte of the sodium-sulfur battery is provided and a gap parallel to the direction of current flow is provided in the positive electrode plate, a gap through which the active material can pass is provided in the positive electrode plate without increasing the resistance value of the positive electrode plate.
When a conductive negative electrode plate is provided in the negative electrode chamber of a sodium-sulfur battery in parallel with the partition, even if the sodium in the negative electrode chamber is consumed and the battery is inclined slightly, sodium is surrounded around the partition by capillary action between the negative electrode plate and the partition. Remains until the end, and the resistance value of the negative electrode chamber is suppressed to a low value even at the end of discharge.

When the negative electrode plate of the sodium-sulfur battery is connected to the negative electrode can by a conductive column or plate and the positive electrode plate is joined to the bottom of the positive electrode can, the resistance value between the negative electrode can and the partition wall can always be kept low. By aligning the center line of the negative electrode plate and plate of the negative electrode chamber and the electrolyte so that they are aligned in a straight line, the current can flow through the battery in a straight line from the negative electrode can to the positive electrode can, and the resistance of the battery The battery can be connected vertically in series.
When the negative electrode plate of the sodium sulfur battery is joined to the negative electrode can, the negative electrode extending from the positive electrode can to the end of the positive electrode can is joined to the outer surface of the negative electrode can, and the positive electrode plate is joined to the side surface of the positive electrode can. Can be connected in series horizontally.

When the partition and the negative electrode can of the sodium-sulfur battery are L-shaped, the sodium channel and the negative electrode chamber are connected by a hole formed in the side of the partition, and the positive electrode plate is joined to the side of the positive electrode can, one side of the battery becomes the negative electrode Thus, a current flows in a straight line in the battery and a battery having a low resistance value is obtained, and the batteries can be connected in series in the horizontal direction.
When iron-based metal or iron-aluminum plywood is used for a sodium-sulfur battery can, a high strength can be obtained even if the can is thinned, and as a result, the weight of the battery can can be equal to or less than that of a can such as aluminum. In addition, using iron-aluminum plywood can reduce the electrical resistance of the can while maintaining strength.

When a metallized layer is formed on the end face of the partition wall of the sodium-sulfur battery and the can and the metallized layer of the partition wall are welded, a sodium-sulfur battery having high joint strength and impact resistance can be obtained.
After the assembly of the sodium-sulfur battery can be plated, the inside of the positive electrode chamber is plated, so that the damaged portion of the welded portion or the like is repaired by the plating layer. Further, the connection layer and the positive electrode plate are connected and fixed by plating, and the resistance value is also lowered.
If the outer shape of the sodium-sulfur battery is rectangular and the outer periphery other than the surface that serves as the electrode of the battery is insulated, a large number of batteries can be stacked in each direction at high density without other insulating materials. In addition, the laminated batteries are integrated as a rigid body and are less likely to vibrate.

Sectional drawing of a battery. (Example 1) Electrolyte shape diagram. (Example 1) The fragmentary sectional view of electrolyte. (Example 1) The end surface sectional drawing of a partition. (Example 1) Sectional drawing of an L-shaped battery. (Example 2) Sectional drawing of an electrolyte extrusion nozzle. Example 3 Sectional drawing of a horizontal connection battery. Example 4

Embodiments of the battery of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view of a sodium sulfur battery.
The battery 1 is a container for the battery 1 by welding a negative electrode can 3 from above and a positive electrode can 10 from below to an insulating partition 7 made by sintering alumina or the like. The negative electrode can 3 becomes a negative electrode chamber and contains sodium 4, and the positive electrode can 10 becomes a positive electrode chamber and contains sulfur 11 and sodium sulfide 12. The sulfur 11 is separated from the sodium sulfide 12 and has a low specific gravity, so that it floats on the sodium sulfide 12.
Four plate-like electrolytes 14 are joined to the partition wall 7, and the electrolyte 14 has an area about twice that of a conventional bag tube electrolyte. The partition wall 7 has a sodium passage hole 6 and is connected to a sodium flow path 13 at the center of the electrolyte 14 to enable movement between the negative electrode chamber of the sodium 4 and the electrolyte 14 due to charge / discharge, and a current path. It also becomes.

In the battery 1, most of the sodium 4 is accommodated in the negative electrode chamber blocked by the partition wall 7, and the volume of the electrolyte 14 is minimized.
A plurality of pillars 2 are welded to the upper bottom inside the negative electrode can 3, and a negative electrode plate 5 is welded to the other end of the pillar 2 so as to contact the partition wall 7. The column 2 and the negative electrode plate 5 are the shortest path of charge / discharge current in the negative electrode chamber. Since the current in the negative electrode chamber does not flow along the outer periphery of the negative electrode can 3, the negative electrode can 3 can employ a metal having low conductivity such as iron.
The negative electrode plate 5 is slightly curved to serve as a flow path for sodium 4 utilizing a spring mechanism for supporting the column 2 and capillary action. Even if the sodium 4 in the negative electrode chamber is reduced and the battery 1 is inclined, the region sandwiched between the negative electrode plate 5 and the partition wall 7 is supplied until the end of consumption of sodium 4 by capillary action.

The vapor pressure of sulfur 11 in the positive electrode chamber of the battery 1 is received by the pillar 2, and the partition wall 7 supports the pillar 2, so that repeated fatigue of the partition wall 7 is reduced and the thickness of the partition wall 7 can be reduced.
A positive electrode plate 15 is provided in parallel with both surfaces of the electrolyte 14, and the positive electrode plate 15 is bent and welded to the bottom of the positive electrode can 10 to reduce the resistance value between the positive electrode can 10 and the electrolyte 14. A large number of gaps parallel to the direction of current flow are provided in the positive electrode plate 15 by processing the positive electrode plate 15 into alternate corrugations, so that sulfur 11 and sodium sulfide 12 can pass through the positive electrode plate 15 through the gap. The gap is formed without increasing the resistance value of 15.

Since the current in the positive electrode chamber does not flow along the outer periphery of the positive electrode can 10, the positive electrode can 10 can employ a metal having low conductivity such as iron.
By arranging the pillar 2 and the electrolyte 14 along a straight line, the resistance value in the vertical direction of the battery 1 is minimized, and the battery 1 can be stacked vertically with a low resistance value.

When the amount of sodium 4 accommodated in the battery 1 is increased, the current density is reduced even if the sulfur 11 is exhausted, but the discharge continues and the electric capacity per weight of the battery 1 can be increased.
The outer periphery of the battery 1 other than the electrode of the can is insulated by an insulator 16, and the batteries 1 connected in series without any additional insulating material can be arranged in three dimensions. Moreover, since the battery 1 is rectangular and the cans are in wide contact between the adjacent batteries 1, they are connected with a low thermal resistance, and the temperature of the arranged batteries 1 is made uniform. The rectangular battery 1 can be closely accommodated in the space, can realize a high electric capacity per volume, and at the same time can maintain high rigidity as a whole.

FIG. 2 is a view of the electrolyte 14 and the partition wall 7 having various shapes when the battery 1 is viewed from below.
In FIG. 1, the electrolyte 14 is premised on the type shown in FIG. 2-A, but the electrolyte 14 can have various shapes as shown in FIG. When a honeycomb type is used as shown in FIG. 2C, high strength can be realized, but the positive electrode plate 15 is also complicated.
When the linear or cylindrical electrolyte 14 is employed, the shape of the positive electrode plate 15 can be simplified and the battery 1 can be easily assembled. The cylindrical electrolyte 14 makes it easier to maintain the contact between the electrolyte 14 and the positive electrode plate 15 by connecting the end face of the positive electrode plate 15 in a circular tube shape.

As shown in FIG. 2E, a part of the cylindrical electrolyte 14 is notched to facilitate the flow of sulfur 11 and sodium sulfide 12 in the upper part of the positive electrode chamber, and the sodium sulfide 12 due to the characteristic difference of the electrolyte 14. Can eliminate the depth difference.
In FIG. 2G, a large number of rod-shaped electrolytes 14 having a single sodium channel 13 are arranged. The rod-shaped electrolyte 14 can minimize the volume per unit area of the electrolyte 14.
The partition wall 7 and the electrolyte 14 can be sintered at the same time, or can be separately sintered and assembled and joined together with glass or the like.

FIG. 3 is a partial cross-sectional view of the electrolyte 14 and the positive electrode plate 15.
More specifically, the electrolyte 14 is provided with a porous insulating layer 14b around the beta alumina electrolyte 14a, and a porous connecting layer 14c outside the insulating layer 14b. A porous support layer 14d is provided inside the electrolyte 14a. There are a plurality of sodium channels 13 in the support layer 14d, and the sodium channels 13 are separated by the legs 14e of the support layer 14d.
The plate-like sodium channel 13 is formed by forming the leg portion 14e into a columnar shape instead of a continuous wall. If only a single sodium channel 13 is used, a rod-shaped electrolyte 14 is obtained.
Sodium ions can pass through the beta alumina electrolyte 14a according to the electric field applied to the electrolyte 14a, and the sulfur 11 and sodium sulfide 12 are blocked by the electrolyte 14a to separate the positive electrode and the negative electrode. The mobility of sodium ions is inversely proportional to the thickness of the electrolyte 14a.

The insulating layer 14b is a porous layer obtained by sintering an insulating material such as alumina, and insulates the electrolyte 14a from the connection layer 14c. The gap of the insulating layer 14b is filled with sodium sulfide 12, and the low-conductivity sodium sulfide 12 serves as a current flow path. Therefore, the insulating layer 14b is thinned to suppress the resistance value.
The connection layer 14c is a porous layer obtained by mixing and sintering an insulating material such as ceramic and a conductive material such as graphite or a refractory metal. The insulating material is a flow path of sodium sulfide 12, and the conductive material is made of sulfur 11. It becomes a flow path. The conductive material of the connection layer 14c also plays a role of reducing the resistance value between the positive electrode plate 15 and the electrolyte 14a.

The support layer 14d is a porous layer obtained by sintering ceramic, graphite, refractory metal or the like, and sodium 4 can freely pass through. The support layer 14d receives the vapor pressure of sulfur received by the electrolyte 14a. Therefore, the thickness of the electrolyte 14a can be reduced to the limit as long as durability can be maintained, and the resistance value of the electrolyte 14a can be greatly reduced. The fluidity of the sodium 4 can be secured by multilayering of the support layer 14d, etc., and the sodium flow path 13 can be eliminated to make the support layer 14d as a whole.
When zirconia, titanium, titanium alloy or the like having a higher thermal expansion coefficient than the electrolyte 14a is adopted for the support layer 14d or the connection layer 14c, the support layer 14d or the connection layer 14c contracts after sintering, and compressive stress acts on the electrolyte 14a. Crack growth of the electrolyte 14a can be suppressed.

When a material having high toughness is used for the support layer 14d and the connection layer 14c, an electrolyte 14 that can receive an impact at the support layer 14d and the connection layer 14c and can withstand an impact at the time of a collision of an automobile is obtained. Compared with, safety is increased. In the electrolyte 14 at the end of discharge, current concentrates on the upper part and generates heat. Therefore, a material having high thermal conductivity and toughness is preferable for the support layer 14d and the connection layer 14c, and beryllium oxide, graphite, molybdenum and the like as materials that can withstand sintering. And tungsten.
Even if the electrolyte 14a is cracked, the electrolyte 14a is surrounded by the support layer 14d, the insulating layer 14b, and the connection layer 14c, so that the electrolyte 14a is not dispersed and the crack does not spread rapidly. Moreover, the sulfur 11 and the sodium sulfide 12 that have entered from the crack react with the sodium 4 to change into the sodium sulfide 12 having a high melting temperature and solidify, accumulate in the support layer 14d and the sodium flow path 13, and eventually close the cracked portion. This contributes to the safety of the battery 1.

There is a positive electrode plate 15 juxtaposed to the connection layer 14c. The positive electrode plate 15 is processed into alternately orthogonal corrugations to provide a gap to form an active material flow path, and in contact with the connection layer 14c at each apex of the corrugation. Yes.
When the connection layer 14c is thickened or a material having a low electric resistance is used to lower the resistance value of the connection layer 14c, the positive electrode plate 15 in parallel with the electrolyte 14 becomes unnecessary, and the positive electrode plate 15 has the tip of the electrolyte 14 and the positive electrode can. It is also possible to focus on the function of communicating with 10 or connect the electrolyte 14 directly to the positive electrode can 10 without using the positive electrode plate 15.

FIG. 4 is a sectional view of the end face of the partition wall 7.
Protrusions 20 are provided on the end faces of the partition walls 7 to facilitate alignment of the can. Moisture of the protrusions 20 is coated with molybdenum particles or the like before the partition walls 7 are sintered to form metallized portions 21. When the metallized portion 21 and the positive electrode can 10 are subjected to chromium spraying or chrome plating, and the negative electrode can 3 and the positive electrode can 10 are welded to the metallized portion 21 with a chromium alloy or the like, high impact resistance and high corrosion resistance are obtained.
The end surfaces of the negative electrode can 3 and the positive electrode can 10 are provided with corrugated irregularities with fine intervals, and the linear expansion of the can is accommodated locally to prevent the weld 8 from being damaged. Further, when the can is welded to the partition wall 7, the partition wall 7 and the can are preheated to 200 ° C. or more and then welded to reduce the residual strain of the weld 8 at the temperature during battery operation.
Since the chromium protective film is damaged by welding 8 when assembling the battery 1 can, the chromium plating solution is poured into the positive electrode chamber from the sulfur inlet after assembly, and the plating electrode is inserted through the sulfur inlet and subjected to additional plating. To repair. Further, when additional plating is applied, the connection layer 14c and the positive electrode plate 15 of FIG. 3 are connected by plating, and are fixed and stable, and the resistance value is also reduced.

FIG. 5 is a cross-sectional view of the battery 1 having the L-shaped partition wall 7.
FIG. 5 is a cross-sectional view of the electrolyte 14 at the center position. In the battery 1, the positive electrode chamber and the negative electrode chamber are separated by an L-shaped partition wall 7, and the negative electrode can 3 and the negative electrode chamber are also L-shaped. The electrolyte 14 is joined to the L-shaped partition wall 7, and there is a thin plate-like sodium channel 13 inside the electrolyte 14, and the electrolyte 14 covers the periphery of the sodium channel 13 so as to sandwich the sodium channel 13. ing.
The electrolyte 14 has a plurality of legs 14 e and keeps the distance between the electrolytes 14 covering the sodium flow path 13 constant.

The sodium flow path 13 communicates with the negative electrode chamber through the sodium passage hole 6 of the partition wall 7 so that movement between the electrolyte 14 of the sodium 4 and the negative electrode chamber accompanying charging / discharging is possible.
The positive electrode plate 15 is joined to the right side of the positive electrode can 10, the positive electrode plate 15 is in contact with the electrolyte 14, and a charge / discharge current flows laterally between the left side of the negative electrode can 3 and the right side of the positive electrode can 10.
When the whole or a part of the horizontal portion of the partition wall 7 is inclined, or a groove is dug or a plate or mat is laid, the sodium 4 is consumed and the sodium 4 is supplied to the sodium passage hole 6 even when the battery 1 is inclined. it can. In the battery 1 of FIG. 5, a sodium passage hole 6 is also provided at the right end of the partition wall 7.

The shape of the sodium flow path 13 is made with wax or the like, each material of the electrolyte 14 is applied around the wax, the applied electrolyte 14 and the partition wall 7 are assembled, heated, and the wax is washed away and then sintered. An electrolyte 14 bonded to the partition wall 7 is prepared. The electrolyte 14 and the partition wall 7 can be separated and sintered, and then assembled and joined with glass or the like.
The space between the left side of the partition wall 7 and the negative electrode can 3 can be narrowed, and the space is always filled with sodium 4. Therefore, when a plurality of sodium passage holes 6 are provided, the resistance value between the electrolyte 14 and the left side of the negative electrode can 3 is It can be suppressed to a low value.
The outer periphery of the battery 1 other than the electrodes of the can is insulated by an insulator 16. Between the adjacent batteries 1, the right side of the positive electrode can 10 and the left side of the negative electrode can 3 are in contact, and the batteries 1 can be connected in series in the lateral direction.

FIG. 6 is a cross-sectional view of the extrusion nozzle for the electrolyte 14.
Each material of the electrolyte 14 fluidized with an organic additive or the like is pressed with a plurality of synchronized screw compressors or the like that match the volume of the material, extruded from the nozzle 17 to form the electrolyte 14, and cut after drying. Seal and sinter the end face.
The sodium channel 13 is made of a material that dissolves and evaporates during sintering, such as paraffin, and becomes a cavity after sintering. After the sodium 4 is injected, sodium occupies the sodium channel 13.

The electrolyte 14a is made of fine particles so as to have a dense structure after sintering. The parts other than the electrolyte 14a are made of large particles, and a sacrificial material such as sodium chloride is included in the material, and the sacrificial material is dissolved and evaporated during sintering to become porous.
When extruding the electrolyte 14, if the electrolyte 14 is extruded and cut using a molded product before sintering of the partition walls 7 as a tray, the labor of assembling them can be saved.

FIG. 7 is a cross-sectional view of the horizontally connected battery 1.
The electrolyte 14 has a plurality of thin rod-shaped sodium channels 13 and communicates with the negative electrode chamber through sodium passage holes 6 formed in the partition walls 7. The negative electrode plate 5 of the battery 1 is welded to the negative electrode can 3. The positive electrode plate 15 is welded to the right side surface of the positive electrode can 10. A negative electrode 9 is welded to the left side surface of the negative electrode can 3, and the negative electrode 9 is insulated from the positive electrode can 10 by an insulator 16. If an aluminum or copper can is employed, even if the positive electrode plate 15 is welded to the bottom of the positive electrode can 10, a current flows with a low resistance value through the positive electrode can 10 to the side surface.
The outer periphery of the battery 1 other than the electrodes of the can is insulated by an insulator 16. The batteries 1 can be connected in series in the lateral direction by contacting the right side surface of the positive electrode can 10 and the negative electrode 9 between the adjacent batteries 1.

The present invention makes it possible to use a sodium-sulfur battery as a power source for automobiles and the like that require high current density and reliability.

1 battery, 2 columns, 3 negative electrode can, 4 sodium, 5 negative electrode plate, 6 sodium passage hole, 7 partition, 8 weld, 9 negative electrode, 10 positive electrode can, 11 sulfur, 12 sodium sulfide, 13 sodium channel, 14 electrolyte, 14a Electrolyte 14b Insulating layer, 14c Connection layer, 14d Support layer, 14e Leg 15 Positive electrode plate, 16 Insulator, 17 Nozzle, 20 Convex, 21 Metallized part

Claims (17)

  In a sodium-sulfur battery using sodium as the negative electrode active material and sulfur and sodium sulfide as the positive electrode active material, the outer shape of the electrolyte separating the positive electrode and the negative electrode is made into a rod shape or plate shape, and single or multiple rod-like thin sodium at the center of the electrolyte A sodium-sulfur battery comprising a flow path or a thin plate-shaped sodium flow path.   A sodium-sulfur battery characterized in that the plate-like electrolyte according to claim 1 is bent, branched or joined.   The interior of the sodium sulfur battery is divided into a negative electrode chamber and a positive electrode chamber by a partition, and an arbitrary number of the electrolytes of claim 1 and claim 2 are joined to the partition and held in the positive electrode chamber. A sodium-sulfur battery characterized by being connected through a plurality of holes.   A sodium-sulfur battery comprising a porous support layer on the negative electrode side of an electrolyte of a sodium-sulfur battery.   A sodium-sulfur battery characterized in that a porous insulating layer is provided on the positive electrode side of an electrolyte of a sodium-sulfur battery, and further a porous connection layer obtained by mixing an insulating material and a conductive material is provided thereon.   A sodium-sulfur battery characterized by adopting a material having high toughness or a material having high thermal conductivity for the support layer of claim 4 or the connection layer of claim 5.   The sodium flow path of the sodium sulfur battery, the electrolyte, the support layer of claim 4, the insulating layer of claim 5, and all or a part of the connection layer are formed at one time by extrusion, and sintered to be integrated. The manufacturing method of the electrolyte of a sodium sulfur battery.   A method for producing an electrolyte and partition walls of a sodium sulfur battery, wherein the electrolyte and partition walls of a sodium sulfur battery are simultaneously sintered and integrated.   A sodium-sulfur battery comprising: a positive electrode plate parallel to an electrolyte of a sodium-sulfur battery; and a plurality of gaps parallel to a direction of current flow in the positive electrode plate.   A sodium-sulfur battery comprising a negative electrode chamber of a sodium-sulfur battery and a conductive negative electrode plate provided in parallel with a partition wall.   A sodium-sulfur battery, wherein the negative electrode plate of claim 10 is connected to a negative electrode can by a conductive column or plate, and the positive electrode plate is joined to the bottom of the positive electrode can.   The negative electrode plate of claim 10 is bonded to a negative electrode can, a negative electrode insulated from the positive electrode can and extending to the end of the positive electrode can is bonded to the outer surface of the negative electrode can, and the positive electrode plate is bonded to the side surface of the positive electrode can. Sodium sulfur battery.   4. The sodium sulfur battery according to claim 3, wherein the partition wall and the negative electrode can are L-shaped, the sodium channel and the negative electrode chamber are connected to each other through a hole formed in the side surface of the partition wall, and the positive electrode plate is joined to the side surface of the positive electrode can. .   A sodium-sulfur battery characterized by adopting iron-based metal or iron-aluminum plywood for the can of sodium-sulfur battery.   A sodium-sulfur battery characterized in that a metallized layer is formed on the end face of a partition wall of a sodium-sulfur battery, and the can and the metallized layer of the partition wall are welded.   A method for plating a sodium-sulfur battery, comprising: plating the interior of the positive electrode chamber after assembling the can of the sodium-sulfur battery.   A sodium-sulfur battery characterized in that the outer shape of the sodium-sulfur battery is rectangular, and insulation is applied to the outer periphery other than the surface to be the electrode of the battery.

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