JPH05507172A - Cathode electrode structure for sodium sulfur battery and its manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Cathode electrode structure for sodium sulfur battery and its manufacturing This article relates to the cathode battery structure of the Ou battery.

In sodium-sulfur batteries, the solid electrolyte material, typically β-alumina, is Molten Sodium/Sodium Polysulfide Cathode Reactant to Form Anode Separate the systems. When the battery is discharged, the above sodium becomes an anode of the solid electrolyte. The sodium ions release their electrons at the interface of the electrolyte, and the sodium ions pass through the electrolyte. It reaches the cathode which is in contact with 1liI on the opposite side. The above electron passes through the above sodium to the anode current collector and from there through an external circuit to the battery's cathode region. to the cathode current collector located in the area. This electron is the cathode current collector must enter the cathode region adjacent to the surface of the solid electrolyte, where this react with the sulfur to form sulfide ions. This sulfide ion and sodium Thorium ions form polysulfides. Since the electronic conductivity of molten sulfur is low, , actually filling the above cathode region with fibrous carbon or graphite material; This fibrous material forms a matrix that provides the desired electronic conductivity. The cathode reactant is transferred from the gas.

Sodium-sulfur batteries usually have a cylindrical shape, and they have a central sodium This may be of the type known as a pond, in which sodium is passed through an electrolyte tube. The cathode region is located inside the electrolyte tube above and the cylindrical current collector and the cylindrical current collector forming part of the battery housing. You can stay there. Instead, the above battery is a type known as a central sulfur battery. The sodium may be placed on the outside of the electrolyte tube. Yes, the cathode reactant is connected to the inner surface of the electrolyte tube and the current collector in the center. – Located in the annular region between the rod or tube. Each of these structures In this case, the cathode region has an annular shape. This cathode region Graphite felt was typically used as the secondary conductive filler material.

Such felt can be formed, for example, into an annular member, and The area can be filled axially. This felt is then impregnated with sulfur. be done. For example, British Patent Nos. GB-A-1472975 and GB-A-151 3682, preforming by compression while impregnated with liquid sulfur. form a shaped member and press this member to fit within the annular area of the cell. A method of manufacturing a cathode matrix by cooling is disclosed. Made by batteries When raised to dynamic temperatures, the sulfur melts and compresses the fibrous material. expands to make good contact with both the current collector and the electrolyte surface.

In U.S. Pat. No. 4.076.902, graphite fibers are located in the annular area between the ta-alumina electrolyte tube and the surrounding battery housing. , whose fiber is connected to the cathode current collector constituted by the battery housing. the fibers extend in a direction perpendicular to the electrolyte tube. It extends perpendicularly to the bar. The above radial fibers are radially conductive Although it has long been considered desirable for improving sexual performance, the US patent There is no disclosure of how to orient graphite fibers in this way. It wasn't shown. One method for radially orienting fibers is patented in the UK It is disclosed in GB-B-2042244. In this specification, electronic transmission A compressible block of conductive fibrous material with fibers spread preferentially in parallel planes This block is cut in multiple parallel planes perpendicular to the above one plane, and all at least one note in which all fibers have a component in a direction perpendicular to the note plane; form. This notebook is then placed in the plane of the sheet with a set of notes extending across it. along parallel regions to form trapezoidal segments between the compressed regions. fiber The fiber has a component in the direction perpendicular to the parallel planes of its trapezoidal section. This fiber sheet Before or during compression, the cathode reactant is exposed to a temperature at which the reactant is liquid. to impregnate. This compressed impregnated sheet is cooled to solidify the reactants. .

Trapezoidal segments are thus made up of multiple segments that can be assembled together forming an annular cathode, each extending at least a portion of the length of the battery; form a field electrode structure.

In British Patent No. GB-B-2095026, Place on the side! A preferred fibrous sheet having fibers of The preferred cathode structure is formed by cut into long strips and bend each strip substantially 90 degrees to its longitudinal axis. , assemble the strips into a sorted structure and arrange the above sheets in a set of parallel regions. A series of parallel grooves are sloped that compress the structure and define the segments of the trapezoidal section. The fibers are positioned perpendicular to the parallel planes of the trapezoid. This group The solid is finally impregnated with liquid sulfur or sodium polysulfide.

This polysulfide is cooled and solidified into grooves that can be used as hino Thus forming a trapezoidal mat connected to each other, an annular mat inserted into the battery form a cathode member.

One of the objects of the invention is to develop a cathode structure for a cylindrical sodium sulfur battery. An improved method for forming fibers between the electrolyte surface and the current collector. It is intended to provide something that extends in the radial direction.

Another object of the invention is to provide an improved apparatus for manufacturing cathode structures. There is a particular thing.

According to one aspect of the invention, forming the cathode structure of a sodium sulfur battery is an electronically conductive fibrous material with fibers that preferentially spread parallel to a certain plane. Cut the sheet into multiple strips and combine the strips into at least one form a sheet-like structure, in which the direction perpendicular to the plane of the above-mentioned sheet-like structure There are fibers that have preferential components, and this structure can be shaped and compressed to forming at least one cathode component, the component forming the cathode structure; a component comprising at least a portion of the desired shape of the component and compressed by the cathode reactant. It consists of impregnating it with.

The above-mentioned forming is performed by compressing the above-mentioned sheet structure in a mold. Good. This mold is preferably at least as desired for a single cathode structure. Preferably, it is configured to simultaneously form a number of components.

The fibrous material notebook has its uncompressed thickness between 0.05 and 0.04 mm during the above cutting process, preferably or 01 to 03, more preferably compressed to 02.

In a preferred embodiment of the invention, the cutting strip of said sheet is The sheets are successively pushed into the holding device transversely to the plane and constitute the sheet structure. Ru. This holding device holds the notebook-like structure in a compressed state during further manipulation.

Preferably, it is parallel to one of the large surfaces of the sheet-like structure and is twisted. At least one yarn, preferably a plied graphite yarn, is threaded through the strip. The strips may be bound together by bonding them together.

Preferably, said sheet is formed exclusively from carbon fibrous material. It is preferable that the fibrous alumina material be combined with the fibrous alumina material before the cutting process.

According to the present invention, in forming a cathode structure for a sodium sulfur battery, A sheet of conductive fibrous material (with fibers preferentially parallel to a certain plane) A layer of fibrous alumina material is bonded to the layer, and the bonded sheet is placed against the surface. cut into vertically extending strips and place the strips in a holding device. and the holding device maintains the strip in compression, at least The strips are connected to each other by a single thread, and the connected strips are is transferred under compression from said holding device to a forming means, and said bonded cut and shape the material into side and base components, and insert the components into the casing. a part of the desired shape of the board structure, and liquid sulfur or sulfide is added to the formed component. impregnated with sulfur or sulfide and held in a compressed state until the sulfur or sulfide solidifies. The present invention provides a method.

According to the invention, furthermore, forming a cathode structure for a sodium sulfur battery Provide equipment. This device is used to cut conductive fibrous material into strips. cutting means for threading the strips and joining them together; The above-combined strips form a small (and also-component) component for the cathode structure. Hand cut the above strip with an in-ejection mold means to form it from the stage to said coupling means, and from said coupling means to molding means, and It is provided with a holding means for compression.

Preferably, the device further indexes the fibrous material in an indexed manner. It is preferable to provide a supply means for supplying the sheet to the casoteng means.

Preferably, the feeding means further applies a fibrous atom to the sheet of fibrous material prior to cutting. means for binding lumina material and feeding it in an indexed manner to said cutting means; It is good to have the following.

The feeding means comprises at least one conveyor driven in an indexing manner. It is preferable to

In a preferred embodiment of the invention, the cutting means is a vertically movable cutting blade. a sheet of fibrous material as described above, comprising a cord and a vertically movable compression block; It is better to compress the

Preferably, the cutting means further comprises: determining the cutting length of the strip of fibrous material; an adjustable stopper for holding the holding device transversely to the plane of the sort; It is advantageous to have a feed plate that presses into the two-cut string.

The coupling means comprises at least one hollow needle, which is located within the retaining device. having a continuous thread passed through the strip which is in a state of compression at the It may be a needle that remains and withdraws from there. This holding device is After falling, the above thread can be cut at either end of the strip row. Preferably, the cutting plate includes a pair of cutting plates.

Furthermore, the above-mentioned holding device includes a 7-year soter that can be opened and a sorting structure held therein. Conveniently, extrusion means are provided which are capable of expelling the product.

The molding means may be a cavity mold having a plurality of island portions and valley portions. The shape is obtained by cutting and molding the above combined strips into the desired shape. It is preferable that the This molding method uses liquid sulfur or sulfide. Preferably, means are provided for pouring into the closed mold.

In a preferred embodiment of the present invention, the above-mentioned device! furthermore the above cutting, joining and modeling. means for moving the holding device between the holding means and for positioning the holding device therewith; It is preferable to have a means of protection.

Preferred embodiments of the invention will be further described with reference to the accompanying drawings.

Figure 1 shows the typical configuration of a 1-IJ ium-sulfur cell growing cathode structure. Ru.

FIG. 2 shows a cathode structure formed for a sodium sulfur battery according to the present invention. 1 is a perspective view of a sheet of carbon fiber material; FIG.

Figure 3: The strips of carbon fiber material shown in Figure 2 are removed during the formation of the above carbon structure. A carbon-alumina composite is an intermediate product manufactured from a carbon-alumina composite. It is a diagram.

4 is an end elevation view of the carbon-alumina composite of FIG. 3; FIG.

Figures 5 and 6 show the construction of a device for forming the cathode structure of a sodium sulfur battery. FIG.

Figure 7 shows the feeding and cutting stations in the process of the apparatus of Figures 5 and 6. Figure 2 is a partial side view, with portions omitted for clarity.

FIG. 8 is a side view of other parts of the feed and cutting station 7 of FIG. 7, for clarity. Some parts have been omitted.

Figure 9 is the Kanji version of Figures 5 and 6 above! The smell is from one station to another Indicating the relative position of the transfer tool for moving material to the station to other machining stages FIG. 8 is a diagram similar to FIG. 8 in FIG.

FIG. 10 is a cross-sectional side view of the transfer tool.

East Figure 10a is a bottom view of the transfer tool in Figure 10, with the basin yatter removed. Indicates the condition.

FIG. 11 is an end sectional view taken along line XI-XI of the transfer tool of FIG. 10.

Figures 12a, b, c and d are the sides of the transfer tool of Figure 9 at the bonding station. This is a top view, with some parts omitted for clarity.

Figure 13 shows the lower cavity mold of the mold cavity filling sedation. FIG.

Figure 14 shows the XI V-X I V line section of the lower cavity mold in Figure 13. FIG.

Figure 15 is a partial sectional view taken along line xv-xv of the lower cavity mold in Figure 13. Ru.

Figure 16 shows the XV I-XV I line section of the lower cavity mold in Figure 13. FIG.

Figures 17a, b, c, d and 0 show the filling station of the mold cavity. The location of the transfer tool in Figure 10 for a certain section! FIG.

Figures 18a, b and 18 are side views of the cathode structure.

Figures 19a and 19b are various views of the base portion of the cathode structure.

FIG. 1 depicts a typical sodium sulfur battery 5, which has an outer case 9. It has a sodium electrode 6, a beta alumina electrolyte 7 and a sulfur electrode 8.

This sulfur electrode 8 is a graph of sulfur, carbon fiber, and alumina fiber. It is a composite structure made of carbon fiber yarn, and each electrode 8 is manufactured by the manufacturing method detailed below. As shown in FIG. 18 abc and FIG. 9 ab, the three side members 70 and It is made from two base members 71.

According to FIG. 2, a sheet 10 of fibrous conductive material is shown. has fibers 12 lying in a plane parallel to the plane of the sheet shown in this example. , parallel to each other and parallel to line A-A. carbon fiber material Fibrous materials of this nature are commercially available in sheet form. In that sort Substantially all of the fibers have at least a directional component extending in a predetermined direction. Ru. In a preferred embodiment, the material comprises a non-woven structure and has a thickness of about 3 Qmm. It is formed in layers. This sheet 10 is a battery for the sodium sulfur battery 5. This is the starting material for forming the sword structure 8.

Carbon material sheet 10 is used to form carbon-alumina composite 14 (See Figures 3 and 4). This is a saw made of fibrous alumina material 15. layer 17 is made of graphite. It is held together by a woven yarn 16. Strip 11 is from Note 10 The fibers are cut along line 13 and are located perpendicularly on top of each other. All of the bars run in the same direction across the width of the mat and therefore The cloak is oriented. The direction of the fiber 12 is generally indicated by the arrow. ing. Aluminum material 15 or S, AFFIL (product name) is glass fill Similar to tarpaper, useful for improving distribution of cathode reactants . This is because alumina is easily wetted by polysulfides, which Easier than bong material. The graphitic yarn 16 is made of twisted silver, e.g. It is preferable to use a plied yarn of 08 to 1 g, for example, a good breaking load of 6 kg. It has a high tensile strength. The role of this material within the fiber composite structure 14 is forcing the layer of compressed carbon mat 11 by acting as a knot It's there. The entire composite is compressed in the direction of arrow C.

These materials are difficult to handle. The carbon mat 10 has a loose structure. Therefore, it is necessary to enforce this during handling. Furthermore, the fiber 12 is This must be taken into account during handling, as it is subject to physical wear. carbon matte To achieve the required electrical performance from 14, over-compression and Bracketing must be avoided as it will destroy the fiber filament. Must be. This occurs throughout the process where the fiber is cut and/or compressed. Applicable. Contamination of fiber 12 with oil, grease, dust, water, etc. should be avoided because it affects the performance of the resulting mat. Alumina material is It has a very low shear strength and its handling is done under bottom tension. graphite The soft yarn 16 is particularly poor in abrasion resistance.

5 and 6 illustrate an apparatus for manufacturing a cathode electrode structure 8. feeding and cutting station 20, bonding station 21 and mold key. The cavity filling station 22 is described in detail below. The product is shown in Figure 5. and the transport tool 23 in different directions shown as 23a and 23b in FIG. is transported between various stations by.

Although Figures 5 and 6 show linear machining, there are many Improvements are possible.

FIG. 7 shows the feeding and positioning section 20 of the feeding and cutting station 20. a and FIG. 8 shows the cutting section 20b. First, refer to Figure 7. Then, the reel 26 of the carbon mat 10 rotates with respect to the spindle 27 in a known manner. Possibly installed. The installation is carbon 20. Carbon reel 26 on conveyor 2 8, and the conveyor 28 The reel 26 is driven to rewind in the direction of the arrow. Above alumina material The feed 15 is also fed onto a reel 29, which reel is connected by a spindle 30 to the Rotatably mounted on the device. Also, suitable known equipment below the level of the conveyor 28 can be used. A means of attachment may also be used. This alumina material reel 29 is connected to a pair of drive wheels 31 (The alumina material 15 is driven in the direction of arrow E by the rotation of the drive wheel. It is rewound in the opposite direction. The actual mounting of the drive vehicle 31 is known and is not critical to the invention. It is carried out in the style of As shown in FIG. 8, the carbon material and the alumina material 15 encounter each other. to form a plurality of layers 17, carbon] 0 is located at the top and alumina material 15 is located at the bottom. do.

This bonding layer 17 is driven by a second drive conveyor 33 to a cutting station. 22b. The second conveyor 33 is at the same level as the first conveyor 28. It is installed.

These two conveyors 28 and 33 and the drive car 31 are all at the same surface speed. by means of suitable drive and control means. (indexing style). The average indexed length is 5. 7mm to 1 It varies depending on the dimensions of the composite cloak 14 manufactured up to 2 mm. (not shown) The ends of the above-mentioned masotho 10, alumina material 15 and bonded layer 17 and The damage is detected and a signal is sent to the control means mentioned above, which keeps the control running until the problem is resolved. The vehicle 28, 33 and drive vehicle 31 are stopped.

To prevent the bonded layer 17 from becoming misaligned, it should be cut off as it emerges from the reel 26. It is necessary to force the cloak 10 to be fed to the cutting stain 20b.

This enforcement means is not shown, but any suitable means may be used. Also, above By unwinding the cloak 10 at a speed suitable for use, the It is necessary to control the tension. Tennyon Moma in Paper 15 It is necessary to control the unwinding speed of the vapor 15 to match that of the conveyor 33. Match.

Furthermore, to detect defects that occur during the feeding of various materials such as noyaming, mismatch, etc. Detection means may be provided for this purpose.

In another embodiment of the invention, the carbon mat 10 has a width of 8Qmm and a width of 4Q+ m length, each split in half to form two elongated pieces, and the aluminum A layer of Mina fibrous material is inserted between them to form a sandwich shape. This process This may be carried out manually or with suitable equipment. This length The length material is loaded onto a reel and automatically fed into the cutting section of the device, or Handcraft a suitable short length strip on the indexing feeder to feed the cutting section It can be easily located in the industry. 80mm width material and 401 width material at the same time is fed to the cutting section 20b of the device.

A further consideration for the bonded layer 17 of material is that of a double or triple structure. It can be related to either.

According to FIG. 8, the cut portion 20b is illustrated, and the carbon/alumina bond The layer 17 is fed to a stop 35 which has a width such as the width of the strip 11. The length is set to adjust to the desired cutting length of the material. Compression block 36 is It is arranged adjacent to a cutting blade 33, which cutting blade 37 is raised after each cut. It can be moved vertically. The above material 17 is cut to 20% of its natural thickness. It has been found that there is an improvement when cutting in a compressed state. Therefore, the above The compression block 36 is configured to compress the material 17 by the desired amount (see FIG. 9). To! It is mounted so that it can be moved in the vertical direction. Opposite material 17 to cutting blade 37 A shutter 39 is located on the side, and is moved in the direction of arrow F to open and close the passage 41. It is movable. Below this passage 41, as shown in FIG. 9, a transfer tool 23 is installed. It is located. A supply blade 38 is provided above the cutting strip 11 with a cutting blade. The cutting strip 11 is placed adjacent to the board 37 and cuts the cutting strip 11 across the face of said sheet. It is vertically movable so as to be pushed into the transfer tool 23. During operation, the above material 17 is fed below the compression block 36 (also below the blades 37, 38); This continues until stop 35 is reached. In one embodiment of the invention, A single width of bonded layer 17 is cut into strips. Two different widths In other embodiments, the lips are fed to the cutting device simultaneously, in a pair of strips. is disconnected in each operation.

When the shutter 39 is closed, the block 36 and the blades 37 and 3 8 are lowered together until the material 17 is suitably compressed. The cutting blade 37 is The block 36 and feed blade 38 are lowered further down to cut the material. It is in a stopped state. After that, the cutting blade 37 and the supply blade 38 are raised. to release the compression of the cutting strip 11. The shutter 39 then opens the passage 41. When opened, the supply plate 38 moves downwardly to feed the strips as shown in FIG. 11 in the direction of the transfer tool 23.

Said blades 37, 38 and block 36 are connected to hydraulic means or other suitable means. More automatically controlled.

Once the strip 11 is cut, the transfer tool 23 holds and forces it. Become. As can be seen in FIGS. 10 and 11, the transfer tool 23 is attached to the base shaft. The shutter 45 is provided with a housing 44 having a shutter 45, and this shutter 45 moves in the direction of arrow H. The base portion of the housing 44 is slidable and opened. Each end of the above housing has a lug piece 44a connected to the shaft 42 by a bolt or stand. is fixed. Further, the transfer tool 23 includes a fisher bar 43, and the fisher bar 43 The shaft bar 43 is slidably mounted on the shaft 42 by a suitable bearing. , connected to Fischer arm 46 by a shaft arrangement. This fisher Since the bar 43 moves up and down in the vertical direction, the Fisher arm 46 is attached to the housing. It will be raised and lowered within the cage 44. Below this fisher bar 43 is a second bar 4. 8 is located and is slidable with respect to the shaft 42. This second bar -48 is attached to a knife 49, as shown in FIG. Also, this The second bar 48 has a Fischer knob 57 mounted thereon, and the second bar 48 has a Fischer knob 57 mounted thereon. Some relative movement is possible between 43 and 48. But when pushed to the maximum The Fischer bar 43 moves with it. Bar 43 above Means are provided at the upper end of the shaft 42 to prevent the shaft 48 from moving beyond its ends. I'm being kicked.

On one side of the housing there is a single or pair of slots 47, shown in FIG. are shown as a pair of slots), into which the cutting strip 1 is inserted. 1 is pushed. A preselected number of strips 11, usually seven, are transferred to the transfer tool 2. 3, the second bar 48 is pushed downwards and the knife blade 4 9 closes slot 47. This movement is performed manually by the Fisher knob 57. Alternatively, said tool 23 can be connected to a hydraulic system, thereby Can be operated automatically.

In embodiments of the invention that utilize a pair of cut strips, the transfer means 10, 10a and 10a with two slots 47 and a button 46. and FIG. 11.

In an embodiment of the invention, when the transfer tool 23 is thus loaded, moving the material 17 between the cutting station 20 and the joining station 21; Ru. 5 and 6 show the transfer tool 23 between the two stations 2o and 21. A big end brake that rotates the transfer tool 23 90 degrees around the horizontal axis when moved with a chair mechanism for operation in the coupling station 21; 3 illustrates a system for correctly matching complexes 14; This transport The tool 23 does not necessarily have to be moved automatically, and the tool 23 does not necessarily have to be moved automatically, and the It is also possible to manually transfer between the two. Then, it will be transferred to 22 again and the next descent will be carried out. You can also do this.

As an alternative to the linear descent method described above, stations 20.21 and 22 can be The transfer tool 23 may be arranged to be moved on the rotation table 67. This specific In the example, the orientation of the stations 20, 21 and 22 is throughout the operation. The transport tools are properly positioned in the same horizontal plane.

Referring to Figures 12abc and d, the coupling stations 21 are adjacent to each other. A plurality of spools 50 of graphitic yarn 16 are rotatably mounted in contact with each other. It is growing. Figure 12a shows only two such spools 50. the above The composite body 14 has a number of graphite knots 16 along its length ( (See Figure 3). If many knots 16 are required, many spools 50 are provided. available. Also, the same number of needles 51 are provided, one of which is shown in FIGS. 12a and 12b. is shown. This needle 51 extends along the longitudinal direction of the composite 14. All can be actuated simultaneously to form a knot and the length of the complex 14 is Determine the number of 16. One needle as all the above needles operate in the same way. The operations of the spool 51 and the spool 50 will be described. Two strips of material 17 In embodiments in which the strokes are lowered simultaneously, the needle 51 is lowered in both strokes at the same time. The lips 11 are arranged to join.

To prevent abrasion of the graphitic yarn 16, all that it passes through The surface is smooth and well polished, free of hard and sharp protrusions. above The twisting and formation of the knot 16 should all be placed under light tension. This is prevented by to each yarn 16 at the point of knotting and spool release. damage is detected by a detection means (omitted for clarity).

The yarn 16 is only 5 m from the spool 50 through the center of the hollow needle 51. It protrudes from the tip of the needle 52 by about m. This needle 51 has a ram shape (not shown). The movement is guided by the bushing 54, and the movement is guided by the needle 51. Limit deflection.

A portion of the slot 47 of the transfer tool 23 is closed by an insert member 55.

This insert member has a series of holes 58 along its length to accommodate the required The number is the same as the number of knots. Although not shown, when the catch means is in the correct position, Provided for holding the insert member 55 and for shaking out the slot 47. Means may also be provided to facilitate this.

The protruding end of yarn 16 initially folds over the needle tip as it passes through hole 55. When the needle 51 passes through the material 17, it remains in that position. above knee The end of the dollar 51 has the distant #wall 44 of the transfer two m23 and the gearing 53. the protruding end springs back to its original position. multiple clans The spool 56 is located on the opposite side of the transfer tool 23 with respect to the spool 50 as shown in FIG. After the tip of the needle 51 protrudes from the gap 53 of the housing 44, the When positioned on the dirt floor of the ramp 56, it grips the protruding end of the yarn 16. There is. As shown in FIG. 12c, pull down the needle 51 from the transfer tool 23. The yarn 16 then remains fixed. While removing the needle 51, the Suitable means are provided for detecting gripping of the horn 16.

The needle 51 and clamp 56 are moved by hydraulic pressure or other suitable means. may be automatically controlled.

Once it is detected that the needle 51 is fully withdrawn, the brake of the transfer tool 23 is activated. The blade 49 is manually or dynamically operated to cut the yarn 16. for this operation Therefore, the stock material and the remaining knot 16 are separated, and the needle 51 and the remaining knot 16 are separated. is also separated, and the carbon alumina composite prepared at the same time is captured in the transfer tool 23. be done. If the graphitic yarn 16 is sufficiently severed by the first cut, If not, the blade 49 can perform more than one cutting operation.

The transfer tool 23 containing the prepared composite 14 is transferred to the bonding station 21. from the mold cavity filling station 22 automatically or manually. and then positioned relative to the lower mold 60 by suitable positioning features (not shown). Can be attached. Although not shown, a detection means is provided, and before the next action occurs, Ensures correct alignment. The above lower cavity mold is placed in the injection mold machine.

FIG. 13 shows a lower cavity mold 60 having two cavities; One is the base cavity 61, and the second is the side cavity 62. Form the base and side portions of the board electrode.

The side cavity 62 has three island portions 63 and has three divided side portions. minutes, which are necessary for the cathode electrode cord 8. This structure is simple It may be formed within one side cavity 62.

Provide the supply cavity 64 and place it at the entrance! Supplying sulfur or sulfide at 65 to reach each of cavities 61 and 62. The supply cavity 64 and Niziev turbines 66 are installed in both the base and side cavities 61 and 62. and the resulting product can be easily removed from the mold. 1st The layout of the mold 60 shown in FIGS. 3 to 16 is one variation, and The shape of the filling will vary depending on the shape obtained and the number of components required to be manufactured. Ru.

As shown in FIGS. 17a to 17e, from the transfer tool 23 to the cavity molding Transfer of complex 14 to card 60 is as follows.

First, the transfer tool glosser 45 is released to form the exit of the composite fiber buying structure 14. (See Figure 17). When pressure is applied to the upper knob 57, the knife Both the blade 49 and the puller bar 46 move downwardly to remove the composite 14. into the mold cavity, this state is shown as side cavity 62. (See Figure 17C). While leaving the pusher 46 at the position 1 (first 7C), remove the knife blade from the cavity 62 by pulling the knob 57. Pull out the card 49. Complex 14 is thereby released into cavity 62. , the position of the strip 11 is forced to two.

Next, the transfer tool 23 is reset by pulling out the button shear 46. , from the cavity mold 60 before the shutter 45 closes the transfer tool 23. move it. Thereby, the transfer tool 23 is ready for the next fiber handling. It is set to ready (see Figure 17C).

The above injection molding machine (not shown) uses an upper cavity mold. cover and knoll the lower cavity mold. Then via port 65 and inject sulfur into the mold. The upper mold has an island part inside the cavity 62. contacting the top and cutting the composite mat 14 to form three separate parts. or provide a region of reduced thickness to break the final product into three separate parts. make it easier to disconnect. After the injected sulfur has cooled, the upper mold is Remove and lower the side and base segments using Niziev Turbine 66. It is taken out from the mold 60. Inject above to speed up descent Multiple composite fiber manufacturing methods to interface with the molding machine May be used.

The resulting components are shown in Figures 18a, b, c and 19aSb.

Figures 18a, b, c show side sections, three of which are attached to the end 72b of the next section 70. It is arranged with the adjacent end 72a to form a cylindrical ring. No. 19a, 1 Figure 9b shows the base part, the end 73 of which cooperates with the underside 74 of the side part 70. do.

In this manner, the side portion 70 and the base portion 71 are connected to each other as shown in FIG. assembled within the outer casing 9 of the lithium battery 5.

/2ri/ iJ abstract Methods of forming cathode structures for sodium-sulfur batteries preferentially A sheet of electrically conductive fibrous material with parallel running fibers is used. This fibrous material The sheet of material is cut into a plurality of strips to form at least one sheet-like structure. In this structure, the fibers are assembled to form a sheet-like structure. It preferentially has a component in the direction perpendicular to the surface. This structure has at least one Shaped and compressed to form the sword component. This component is small Both consist of sections of the desired shape of the cathode structure. This compressed component is impregnated with a cathode reactant.

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Claims (29)

[Claims] 1. 1. A method of forming a cathode structure for a sodium sulfur battery, comprising: A plurality of sheets of conductive fibrous material having fibers extending preferentially parallel to one plane are Cut to trip, The strips are combined to form at least one sheet-like structure in which the fibers are The structure is formed so as to preferentially have components perpendicular to the surface of the structure, and the structure is molding and compressing to form at least one component, the component being including at least one section of the desired shape of the sword structure; A method consisting of a step of impregnating a reactant. 2. A claim in which the above-mentioned molding is performed by compressing the above-mentioned sheet-like structure in a mold. The method described in Section 1. 3. The mold has at least one desired number of components for the cathode structure. 3. The method according to claim 2, wherein said molding is carried out so that said parts are formed at the same time. 4. Claim 1 further comprising the step of compressing the sheet of fibrous material during said cutting step. 3. The method according to any one of 3 to 3. 5. 4. The sheet is compressed between 0.05 and 0.4 of its uncompressed thickness. Method described. 6. 6. The sheet is compressed between 0.1 and 0.3 of its uncompressed thickness. How to put it on. 7. 6. The method of claim 5, wherein said sheet is compressed to 0.2 of its uncompressed thickness. 8. Further, the cut strip of the sheet is pushed across the sheet surface into the holding device. to assemble the sheet-like structure, and the holding device compresses the sheet-like structure during the next operation. 8. A method according to any one of claims 1 to 7, characterized in that it is maintained in the same state. 9. Additionally, the combined strips are tied by passing at least one thread through them. The threads are bundled and bonded to each other, and the threads are parallel to one of the relatively large surfaces of the sheet-like structure. 9. The method according to any one of claims 1 to 8. 10. 10. The method of claim 9, wherein said yarn is twisted graphite plied yarn. 11. Claims 1 to 10, wherein said sheet is formed preferentially of carbon fiber material. Any method described. 12. Furthermore, before the cutting process, a layer of fibrous alumina material and the sheet are combined. 12. The method according to any one of claims 1 to 11. 13. 1. A method of forming a cathode structure for a sodium sulfur battery, the method comprising: A conductive fibrous material sheet with fibers extending preferentially parallel to one plane. Bond the layers of alumina material and cut this bonded sheet into multiple strips. , The strip is placed in a holding device that holds it in compression, with at least one Thread the threads through the strips to bond them together and place the bonded strips in a compressed state. The combined material is then transferred from the holding device to a forming device, where the bonded material is and mold the molded component into the desired shape of the cathode structure. Classification and non-existence, impregnating the molded component with liquid sulfur or sulfide; A method of keeping it in a compressed state until it solidifies. 14. An apparatus for forming a cathode structure for a sodium sulfur battery, the apparatus comprising: means for cutting the conductive sheet into a plurality of strips and compressing the strips; The strip is placed in a holding device that holds it in place and threads at least one thread through the strip. binding means for joining each other together, and forming the joined strips to form the above-mentioned cathode. injection molding means forming at least one component of the structure; , compressing said strip and passing it from said cutting means to said bundling means; and a holding device for transferring the material from the container to the molding means. 15. further comprising means for feeding said fibrous material to said cutting means in an indexed manner. 15. The device according to claim 14. 16. The supply means cuts the fibrous alumina material into sheets of the fibrous material before cutting. 16. The apparatus of claim 15, wherein means for coupling and feeding the same to said cutting means in an indexed manner. Place. 17. said feeding means comprises at least one conveyor driven in an indexing manner; 17. The device according to claim 15 or 16. 18. The cutting means includes a vertically movable cutting blade and the fibrous material sheet during cutting. and a vertically movable compression block capable of compressing the material. The device described in any of the above. 19. The cutting means is adjustable to further determine the length of the cutting strip of the fibrous material. 19. A device according to any one of claims 13 to 18, comprising stop means capable of stopping. 20. The cutting means further cuts the cutting strip across the face of the sheet. 20. A feeding blade according to any of claims 13 to 19, comprising a feeding blade for pushing into the holding device. equipment. 21. The binding means is threaded through the strip and held in a compressed state by a holding device; Hollow needle holding a continuous thread that can be manipulated to pull down leaving the thread in position 21. The device according to any one of claims 13 to 20, comprising at least one. 22. The retaining device includes a strip that is retained there after pulling down the needle. a pair of cutting blades operable to cut the thread at either end of the thread; 22. The device of claim 21, comprising a radar. 23. The holding device further includes a shutter for opening the holding device and a shutter held therein. Claim 13 further comprising pusher means operable to push out the sheet-like structure. 23. The device according to any one of 22 to 22. 24. The above molding means or a cavity mold having multiple island parts and valley parts. and whose shape forms the combined strip into the desired shape upon closure. 24. A device according to any one of claims 13 to 23, which has a hollow shape. 25. Inside the mold, the molding means further encloses liquid sulfur or sulfide. 25. A device according to claim 24, comprising means for injecting the . 26. Furthermore, the holding device is arranged between the cutting means, the bundling means and the molding means. Claims 13 to 25, comprising means for moving and means for positioning the device relative thereto. The device described in any of the above. 27. Sodium ion formed by the method according to any one of claims 1 to 12 Cathode structure for batteries. 28. A cathode structure substantially as shown in or described in connection with the accompanying drawings. How to form. 29. A cathode structure substantially as shown in or described in connection with the accompanying drawings. A device that forms