JPS62198060A - Slender tube sheet for hollow fiber type battery and manufacture of the same - 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 The present invention relates to a long tube sheet for hollow fiber batteries and a method for making the same.

Hollow fiber batteries, such as IJum/sulfur batteries, traditionally use disk-shaped tube sheets. U.S. Patent Nos. 3,476,062, 3,672,995, 3,697,480, 3,703,412;
No. 3,749,603, No. 3,765,944, No. 3,791,868, No. 3,829,331, No. 3
, No. 917,490, No. 4,050,915, No. 4,
No. 219,613, No. 4,224,386, No. 4,2
No. 96,052, No. 4.334868, and No. 4,
See No. 403°742.

The fibers of the cells disclosed in the latter patents can be open (terminated on the "outer" or "top" side of the tubesheet) or can be closed-ended lengths depending from the inner or lower surface. The open end communicates with the anode chamber and the closed end is immersed in the catholyte with an intervening jacket of aluminum foil for current extraction/distribution. The outer periphery of the tubesheet is in sealing connection with at least the anolyte container, thereby separating the anode and cathode materials. That's N
It is also temporarily non-conductive. The fiber wall is 'permeable' to the cations of the anode material (e.g. melting IJum), and the (conductive) anode material and foil are connected to an external electrical circuit by electrical wires when the cell is in operation. There is.

U.S. Patent Nos. 4,219,613 and 4,296,052
of particular relevance to the present invention. The '613 patent relates to a combination of hollow fiber bundles and helium-tight tubesheets with graded porosity, the latter resulting in better stress distribution over the fibers as they "enter" the tubesheet. . No. 4,296°052 relates to a two-step (pake and broil) process for achieving graded porosity during "firing" of tubesheets, which is the closest approach to conventional firing methods.

There are difficulties in scaling up batteries of the type of the above patents.

For example, it is used in conventional batteries as a result of the particle size that must form the tubesheets used and as a result of the low glass transition temperature of unruder glass, which is considered suitable for the tubesheet manufacturing method used. Disk-shaped tubesheets deform too easily during heating during battery operation. Deformation occurs under the combined influence of gravity and the pressure difference created by mass transfer from the anode chamber to the cathode chamber during the discharge. Although the degree of deformation in a single-discharge half cycle is not large, the incremental deformation is not effectively reversed during battery recharging. Therefore, the deformation accumulates by 1" during the long-term light/discharge cycle of the cell.

This problem (which has not been previously recognized, disclosed, or suggested) is expected to worsen rapidly with increasing tubesheet diameter. It is recognized that deformation as small as about 10 mils (254 microns) can cause fiber failure, and this deformation is a significant impediment to scale-up of cells where the tubesheet is disc-shaped. Dew.

Another obstacle is the difficulty in manufacturing leak-free large-scale assemblies of hollow fiber bundles and disc-shaped tubesheets using the previously disclosed one-way process. In other words, it has parallel fiber lengths.”
When the "rudder", lamp-spacing and fiber-spacing foil tapes and cathode foils are wrapped together around a rotating horizontal core, a portion of the fibers that are to be threaded through the tubesheet substantially exit beyond the core ends. .This protrusion is unsupported and
The tubesheet material (a pasty slurry of glass particles in a volatile liquid medium) is deposited above and below them.

As the spreading roller rotates, the hanging fiber portions are lifted up and further bent and subjected to twisting action. The resulting bending at best disrupts the normal alignment of the slurry and also makes it impossible for the slurry to form a body that is evenly distributed around and between the fibers. It is difficult to make tubesheet/fiber assemblies by this method that does not require some post-firing treatment to prevent leakage. This is especially true for conventional large diameter tubesheets.

It is possible to manufacture disk-shaped tubesheets by methods other than ``bake and broil'', i.e., the advantage of graded porosity within the tubesheet is the reduced leakage paths that occur when the tubesheet is more uniformly densified. It disappears because of it.

However, this requires very precise control of firing times and temperatures in order to achieve proper melting and adhesion of the tubesheet material to the fibers without at the same time closing a significant proportion of the fibers.

It is therefore clear that a tubesheet construction that avoids the above problems would be highly desirable.

Another problem with disk-shaped tubesheets, particularly their very dense versions, is that substantial shrinkage occurs when the liquid slurry medium is removed and densification occurs. The greatest movement due to circumferential and radial contraction occurs at the periphery of the tubesheet, resulting in "cracks." Therefore, as the tubesheet diameter increases, the cracks become so severe that the disc becomes useless for its purpose. However, if the tubesheet material 1' can be reduced, i.e., the interfiber spacing within the tubesheet can be significantly reduced, the corresponding diameter The tubesheet will be very resistant to deformation.However, other problems can be raised. There is a need to hold the ends together, but there is no practical way to do this, especially when scaling up to large diameter assemblies. It is also necessary to carefully slide the sheet further out from the assembly platform, which creates greater leverage and increases curling and bending during rotation even with small amounts of slurry.

In addition, the spherical particles contained together with the crushed glass in the outer dosing slurry are used to neatly align the fiber ends (to improve the extrudability of the paste-like slurry and to effectively pack the particles uniformly into the tube sheet). must be removed. This in turn requires the use of a thinner slurry (for ease of extrusion) and results in greater shrinkage during dry firing of the tubesheet.

It also makes initial retention of the slurry on the rotating fiber "brush" much more difficult.

Yet another obvious difficulty with the use of long or "plug" tubesheet constructions is that the barrel-shaped seals traditionally used to connect the cathode (and anode) cup around the disk-shaped tubesheet require relatively small diameter tubes. Although this seems convenient and attractive for seats, it requires the use of overlapping concentric (sleeve) type seals, which are quite difficult to make distortion-free.

Plug tube sheets will be found to be of substantial safety if something can be done about them. That is, the point of failure of the disk-shaped tubesheet in an active cell can cause direct contact between a relatively large amount of anode and cathode material and a subsequent highly exothermic chemical reaction between the sulfur in the catholyte (e.g. in a sodium/sulfur cell) and the aluminum foil. Various high temperatures are generated which cause extremely violent reactions. Conversely, a plug tube sheet break (at least in a "two-chamber" cell) results in only a very limited amount of anode-to-negative contact.

Therefore, despite the uncertainties posed by the many demonstrated and anticipated difficulties of plug-tube sheet manufacturing, its manufacturing process continues to be investigated.It is therefore a primary object of the present invention to provide a solid hollow fiber battery. The object of the present invention is to provide a type of tube sheet that can be easily manufactured and scaled up. A secondary objective is to provide a convenient and automated method for assembling scaled-up batteries.Another objective is to provide a tubesheet in a shape that can be formed after the fiber bundles have been wound (or formed). be.

Still another objective is to "fire" the tubesheet from the outer surface to the inner surface so that a large temperature gradient that aids in the formation of graded porosity can be obtained by simply heating only the outer edge directly (the remainder being heated by conduction). Our goal is to provide tube sheets of various shapes.

An additional object is to provide a tubesheet structure that is much simpler and can be more uniformly densified under a time/temperature baking process that does not require the use of a vacuum oven.

A further important objective is to provide a tubesheet structure that can be produced with a slurry that does not contain "spherical" or other relatively large and difficult to sinter particles.

It is also an object of the present invention to provide a tubesheet processing method that automatically seals any broken fibers in the raw fiber/tubesheet assembly without relying on post-firing treatments.

Another object is to enable the use of tubesheet glass having essentially the same composition as the fibers.

It is a further object to provide a tubesheet construction which allows the use of low force feed channels to seal between the tubesheet and the anode and cathode cups. The scope of the invention will be apparent to those knowledgeable in this field.The present invention is particularly directed to a generally cylindrical body made of a cohesive slurry of ceramic powder material in a volatile corrugated body compactly assembled together. The unembedded portions of the fibers are in a bundle of 8 m long ceramic hollow fibers (hereinafter referred to as long fibers) spaced apart with their tips embedded in the bundle. The average distance between adjacent attached fibers forming the larger diameter portion of the bundle is /J% from the average distance between adjacent fiber portions forming the larger diameter portion of the bundle.
and the slurry is transformed by drying, heating, and cooling into a solid ceramic tube sheet into which the embedded fibrous portion is encapsulated and forms a composite structure with the embedded portion.

The present invention also relates to methods of making high temperature batteries and hollow fiber/plug tubesheet composite structures using generally cylindrical ceramic tubesheets.

FIG. 1 is a vertical perspective view of successive steps in manufacturing the preferred hollow fiber(s)/tubesheet assembly of the present invention.

FIG. 2 is a vertical cross-sectional view of a two-chamber IJum/sulfur cell incorporating the hollow fiber/tubesheet assembly of the present invention. The battery part is shown as an illustration to show the state of technology.

An enlarged view of the circled portion of FIG. 2 is shown in FIGS. 2A and 2B.

FIG. 3 shows a "single chamber" sodium/sulfur cell incorporating the hollow fiber/tubesheet assembly of the present invention. The outer casing is shown cut in vertical section to reveal the remaining battery components. The battery part representing the technical state is shown as such.

Hollow fiber bundles are formed with free ends in which no fibers are embedded; The slurry is dipped into a substantially cylindrical deposited bundle of coated fibers, i.e., 1 dipped plate, and b. ) or more excess slurry is removed from the soaked brush and preferably C.
, the slurry can rise inside the lumen of the fibers by capillary action (to a height K to the extent that the ends of the fibers can no longer be closed and are torn); (2) the free ends of the fibers are (3) The resulting plug-shaped tubesheet is optionally uniform or more preferred. It has been found that the above object is achieved by the method described above: recoating the whole with the same or a different suitable slurry to form a skin and then drying.

The resulting article has the advantage that it can be dried and heated in a subsequent step according to predetermined time/temperature specifications and in such a way that the tubesheet is transformed into an at least largely ceramized object.

Preferably, there may be no means to prevent slurry infiltration into the fibers. The method also includes the further step of opening all suitable fiber ends embedded in the slurry into the ceramized tubesheet. That is, the outer end portion of the ceramized tubesheet/fiber composite is folded or cut, and the length of the removed portion is such that it includes any tubesheet material that may be present within the lumen of the fiber. , it is not like unblocking unsuitable fibers. The "fired" assembly is helium-tight without further processing.

"Ceramic" is defined in the broad sense set forth in the complete ridges 2nd edition of the Webster. That is, products made from earth (sand, clay, metal oxides, etc.) by the medium of heat, such as glass, enamel and ceramics.

As used herein, "cylindrical" refers to an object whose length to its effective average diameter is at least two or more" and has a geometrically square cross-section, most preferably a circular cross-section. Applies to long objects that may have irregular shapes and/or non-uniform cross-sections.

For convenience, fiber "bundles" as used herein refer to fibers "separately" or spaced apart as parts of an assembly including other components, such as a cathode foil or equivalent current distribution delta extraction means, and insulating tape. Refers to multiple long fibers.

In this specification, "1 immersion" refers to a method in which the fiber end is immersed in a slurry liquid, and then the slurry portion that does not remain on the fiber end is dripped off or removed by other methods while standing the fiber end vertically. There is hail.During the dipping operation, one of the fiber ends
The slurry and/or fiber ends may be vibrated to settle or acquire the slurry throughout the plastic.

As used herein, "1 capillary glass" generally refers to hollow e and m, and to avoid confusion with the meaning of "fiber glass," it mainly refers to glass in which a hollow edge aperture is configured as "1 capillary glass." used.

As used herein, "ceramized" applies to that portion of a fired tubesheet produced by either melting or sintering of particles.

1. The term "at least predominantly ceramized" includes the concept that not all of the tubesheet particles need be sintered.

The temperature condition along the central axis of the tubesheet during firing is such that the particles on the bottom or inside surface of the tubesheet are not sintered, i.e. the bottom part of the finished tubesheet is dry. It may be such that it has the "green" nature of the tubesheet particles, but at the other end the tubesheet particles can all be fused into a single, homogeneous, dense ceramic body.

°Helium-tight means that the molten portion can diffuse less than 10"7" helium through the tubesheet or along the fiber/tubesheet interface (measured under standard conditions)
A tube sheet with an internal structure that is The diffusion rate is an absolute rate and is not expressed as the amount of helium diffused per unit area (per unit time). Helium passes only by leakage, regardless of the tubesheet diameter (if the end of the fiber section descending from the test tube is closed, the presence of cracks, tears or incomplete closure can be tested as a so-called gross leak).

"Suitable fiber end" means an end portion of a fiber that is not broken and is closed (temporarily or permanently) at the other end.

Additionally, the strong distortion-free sleeve-type seal between the plug tube sheet and the anode (and cathode) cup feed passages is designed to provide high resistance between the seal and the ceramicized tube seal material, as well as their glass transition temperatures (Tg). It has also been discovered that it can be effective if well balanced.

If expressed as a non-fired article, the invention may be described as follows: having end portions closely packed together and embedded in a generally cylindrical body of a adherent slurry of ceramic powder material in a volatile liquid. the slurry comprises bundles of spaced ceramic hollow filaments, the average distance between each adjacent end portion being equal to or less than the average distance between each uncollected portion of the filament; The cylindrical body is manufactured by an operation consisting of (1) dipping the fiber end portions in the slurry and limiting the diameter of the resulting "dip brush," and (2) forming a solid ceramic tube sheet by dry heating. The end portion of the fiber that is altered and threaded through it has flowability, wettability, and powder particle size range such that the end portion of the fiber is in sealed connection therewith and forms a composite structure with the end portion.

In a preferred embodiment, the slurry flows into the open fiber ends by capillary attraction to a substantially greater extent than the unsuitable fiber ends and is thus transformed into the composite structure. It is particularly preferred that the fiber "bundle" includes the cathode foil and that the hanging fiber ends are closed. An advantage of the plug tubesheet construction is that the fiber embeddings are closer together and more uniform than in disc-shaped tubesheets.

An additional advantage is that the type of leakage experienced with disc-type tubesheet/fiber assemblies, ie, so-called double leakage, can be eliminated with plug tubesheets. That is, in a disc-shaped tubesheet, if two fibers are not separated by the intervening tubesheet material, #”M
A leakage path is created from one side of the tube sheet to the other along the contact line between #. The high firing temperatures available for plug tubesheets sinter and seal the spaces between the fibers in contact, creating a slight spider layer beneath the outer surface of the tubesheet. Although this may distort the included fiber cross-section,
It is unlikely to cause any significant restriction to the sled lumen.

The large particles in the slurry used in disc tubesheet production are essential to the slurry rheology necessary for the viability of the conventional manufacturing process. However, the elimination of this large particle (generally spherical) is essential to the tight fiber packing of the plug tubes and sheets of the present invention. Fortunately, this omission is more than bearable, and it improves slurry flowability as is essential to plug tubesheet production. Furthermore, it allows for an "automatic" sealing of the end sections if there are unsuitable fibers in the bundle. That is, the particles are small enough that the slurry can flow into the IIA# section opened during the dipping operation by the capillary attraction force 2.

It has also been discovered that it is possible to fabricate fiber and plug tubesheet assemblies using tubesheet materials that have substantially higher glass transition temperatures than those previously available. This is an unexpected result of being able to produce tubesheets from fine particles and from slurries that do not contain the large particles present in conventional slurries.

The present invention is particularly suited for use in hollow fiber type IJum/sulfur batteries, but is generally suitable for use in hollow fiber type high temperature batteries. It is also believed to be convenient for manufacturing and operating hollow fiber type high temperature devices other than batteries.

As noted above, the plug-type tubesheets of the present invention are generally cylindrical and have an sb length to average effective diameter ratio of at least 2.

Although there is no inherent upper limit to this ratio, the more severe the ratio, the more care must be taken in handling it to prevent tubesheet damage. Furthermore, there is no apparent benefit for ratios substantially greater than 10:1, and as the ratio increases, the efficiency of use of materials and battery space decreases by 74%. In practice a ratio of 3 to 6 is highly preferred.

Fibers, tubesheets and sealing phase materials suitable for the practice of this invention can generally be incorporated into ceramics (as defined above).

Other properties of the material selected will vary depending on the specificity of the particular application for which the intended device is being manufactured, but in all cases it will be necessary to accommodate relatively narrow requirements with respect to thermal properties and adhesive properties.

Tubesheet materials can be adapted to additional requirements. llJ
It must be able to be made into a slurry which is not very viscous and has a suitably high solids content. With respect to heat and adhesion, the ceramic particles in the slurry must be heated and cooled to form a substantially continuous ceramic body that sealsly connects the fibers passing therethrough and adheres to the sealing glass. Ceramic body (can be the entire tubesheet or just the “top”)
must be reasonably comparable with both the delicate and generative seal sections in terms of expansion coefficient and have substantially the same glass transition temperature (Tg) as the generative seal section. That is, when the seal portion and tubesheet body cool, they must reach their glass transition points at substantially the same temperature.

The internal moisture content of the glass from which the tubesheet is made substantially affects the Tg of that glass. It is therefore known that when the glass designated "T-Ill" (composition is given in Table 1) is dried (purged with gold while melting) it has a Tg 12° higher than that which is not dried. The Tg of a tubesheet glass can be varied by its component losses exerted on the vapor pressure when kept in a molten state below atmospheric pressure. For example, T-11
1 glass slowly loses HBOz under the latter condition and therefore its Tg increases.

After all, the Tg of the finished tubesheet (or its molten part) is not necessarily the same as that of the glass from which it was made.
That is, milling, slurrying, drying and phosphoricating (sintering) T-111 glass results in a 7g increase of approximately 15°. Therefore T
- The actual Tg of a tubesheet made from glass will be as much as 27° higher than that measured for a starting glass that has not been nitrogen purged during casting and has not undergone the tubesheet processing process.

Sealing glass candidates must possess certain properties to qualify for consideration as a sealing glass between the cup and plug tube sheets. The first requirement is dictated by the seal environment. For example, in a sodium/sulfur battery, the glass must have sufficient chemical resistance to sodium, sulfur, and sodium polysulfides to maintain seal integrity, and be sufficiently viscous at 300" C1! cell operating temperatures to prevent harmful deformation. The properties of the seal must also meet the glass property requirements.The seal glass must form two types of seals: a glass-to-metal seal with the anode cup and a glass-to-glass seal with the plug tube sheet. It must be fluid enough to drip below the cup metal melting point (660° C. for aluminum).

The seal glass versus tube sheet portion of the seal has the most stringent property requirements of the entire seal glass. As will be discussed below, plug tube sheet-sized glass-to-glass sleeve seals are extremely difficult to specify and process, unlike glass, which must maintain an intact seal over a temperature range from room temperature to 300°C. It is.

Due to the influence of the number of manufacturing steps on tubesheet glass, the Tg of sealing glass Tgilt tubesheet is 6.15% higher than the Tg of tubesheet even though both are manufactured from the same batch of glass.
It may be as low as ℃.

It has been discovered that a practical solution to the latter problem is the use of a sealing glass having a somewhat different composition than the tubesheet glass. Thus, a satisfactory comparison between both the Tg and coefficient of linear expansion of the seal and tubesheet is reproducibly observed.

Plug tubesheets containing fibrous portions embedded in the tubesheets can themselves be easily manufactured to a size that can be used as Tg test specimens (defined by the expansion bulk along the tubesheet diameter).

It is possible to use the same composition of tubesheet glass as hollow fibers if the tubesheet is plug-shaped and the slurry produced consists essentially of particles with an effective radius of curvature that is substantially smaller than the fiber lumen. has also been discovered.

As long as the tubesheet glass particles have good point-to-tip contact - localized melting can occur before a single fiber reaches its softening temperature - a suitable continuous tubesheet structure is obtained without occluding the fibers. However, glasses known to be suitable for capillary tubes generally cannot be used as sealing glasses. These are not fluid enough to drip below the melting point of aluminum, although higher melt tank materials can be used.
Unless the sealing glass is heated to form a seal with the tubesheet, the temperatures will be so high that at least the outermost fibers will be occluded.

On the other hand, the Tg of seal glass is the Tg of tube sheet glass.
It is necessary to appropriately balance the g. It is highly preferred to use tubesheet (and seal) glass that has a lower Tg than zero Km fiber glass, which otherwise rarely provides battery life of more than about 1 to 2 weeks.

When sealing wax glass to a tubesheet, raise the temperature until the sealing glass softens enough to stick to the tubesheet. For example, in T-TO glass, 49
A sealing temperature of 5°C for 15 minutes is required (sealing temperature depends on time).0 If the Tg of the sealing glass is lower than that of the tube sheet glass (it is much softer) then the sealing glass will have a stiffer tube during its cooling. Adapts to dimensional changes in sheet glass. Eventually the sealing glass will reach its set temperature, i.e. it will no longer conform to the cooling tubesheet without internal distortion. This is called the seal set point and occurs at the seal glass temperature between the slow cooling point and the glass transition temperature. Furthermore, the sealing glass during cooling is tube sheet glass (this is already the T
(lower than g). The tubesheet/seal composite is therefore undesirably strained. This distortion is unavoidable by slow cooling and continues even under normal usage conditions of high temperature batteries. Unbearable distortion can only be avoided by appropriate balance between the Tg of the seal and the tubesheet □The Tg of the seal and tubesheet must differ by more than about 5°C, and their linear expansion coefficients must also be more than about 10 x 10/'C. I hope it's no different.

Practically all glass seals have some degree of internal distortion at their operating temperatures. A good seal is one that functions properly under the planned operating conditions. For most seals this means a seal strain of 1500 to prevent cracking.
This means that it must be less than psi.

The sealing method involves immersing the end of the supply channel of the tank in molten sealing glass, taking it out and cooling the adhering glass.Of course, this is because the molten glass properly wets the tank material (e.g. aluminum). Since a close balance between the coefficients of expansion of the seal and the tank material cannot normally be maintained, the seal glass is generally required when the cell is at operating temperature (see Figure 2B) to avoid intolerable distortion of the glass. It will be necessary that the portion of the tank in contact with the tank be relatively thin (eg, 5 mils).

Ceramic durable materials that are generally suitable for use as fibers and tubesheets in the practice of this invention include those disclosed in the aforementioned US patents. Patent No. 1602, 1
Nos. 331, 1995 and 1386 are the most descriptive of fiberglass compositions, and 2490, 16
No. 13, No. 1386, and No. 2742 most describe tubesheet compositions. (n) Ceramic materials may also be suitable for the manufacture of high-temperature batteries or non-battery vessels using anode and/or cathode materials other than IJum and/or sulfur.

Special compositions for various combinations of capillary tubesheet and sealing glass resulting in helium tight fiber/tubesheet/anode tank assemblies are described below. The life results of a completed battery with the above assembly are also shown.

Stage A in Figure 1 shows the central aluminum tube shaft (2), the aluminum foil cathode current collector with only the exterior visible;
Distributor (3), many parallel hollow fibers (4
), aluminum isolation tape (not shown, see number (32) in Figures 2 and 2A) and thin 2 aluminum fastening tape coated with pyrolytic adhesive (not shown, Figures 2 and 2A) (35)) is shown. Reference may be made to the '1868 patent for details of the winding process (other than the use of relatively long fibers and the omission of tubesheet material in the assembly).

Only the upper end of the tube axis is shown in stages B to JK.

In stage B, a "1 plastic" (5 in stage A) consisting of exposed portions of fibers (4) (its upper end closed and lower end open) is prepared using various grinding aids such as a liquid such as coumol and hexadecylamine. The pulverized tube sheet glass is partially immersed in a slurry (6). The slurry is placed in a cup (7) and the cup is lifted for immersion. (7) is lowered to allow the excess slurry to drip off the brassino 5 (5), and the brush contains the slurry sent into it by the wicking action and is surrounded by a layer of slurry (8). .

In steps, the assembly (1) is rotated about its vertical axis (by means not shown) while the three 1" (9) are pressed lightly inwardly against the brush and held horizontally. It is vibrated (by means described below) to reduce the effective diameter of the brush, allowing complete and uniform penetration of the slurry into the brush and dripping off any remaining excess slurry.

In stage E the coating (8) has now been substantially reduced in thickness and has two spots <11 on the coated brush.
((10), cotton thread) and ((11), an aluminum thread is attached.The aluminum ring is attached as a ring just below the wooden thread and is pushed down to push the slurry down a little. (The aluminum ring is usually part of the tubesheet that is removed after firing).

In step F, the membrane brush is rotated around its central axis and, if necessary, a human finger or Teflon (E, 1
．． The fiber layers are aligned to correct convergence by means such as a DuPont trademark cylinder ((12), as shown).

In step G, the slurry-laden portion (13) of the brush (5) is dried until it becomes somewhat hard, and then slurry (13) having the same or different composition as the slurry (6) is added.
4).

In step H, the slurry is removed from the assembly and the assembly is briefly rotated several times to remove excess slurry (14) and smooth the new outer layer (15). If there is a slurry tail (16), it can be easily cut with something like scissors.

In stage I, the assembly is rotated in a forced air flow (by fan) to dry & (evaporate the liquid components in the slurry). “Raw” tubesies seen at this stage) (
17) is baked in vacuum to completely remove the liquid slurry medium η and to remove as much grinding aid as possible before stage J.

At step J, the assembly is inverted and the raw tube sheet (17) is placed in the metal heating device (18) for tube sheet firing.
, heat supply and temperature regulation means (not shown).

The vibration and "squeezing" action of the "shoe" used in step (3) of the above method is applied by appropriate means. Preferably methods that are actually used. I quickly attached an ordinary three-fingered experimental clamp to a vertical rod and made improvements in four places: I removed the thumbscrew, removed the spring that would normally push the clamp arm, fixed a direct current relay on the sixth arm, and fixed the groove. A plastic block ("shoe") was screwed onto each of the three fingers (attached by a locking screw).

One of the clamp arms has a shoe with one 1" finger and the other has a shoe on each of its two fingers, which arm can move toward or away from the slurry-laden fiber brush by 1,000. Nominally, a dc current relay is made to "chatter" by applying 45 volts of ac current through its coil (the 1 point of the relay is not used).The composition and manufacturing method of the slurry is generally U.S. Patent Nos. 3 and 9 above
It is by No. 17゜490. U.S. Patent No. 4,219,
No. 613 and No. 4.403.742 are also referred to, but the main point is that the large (spherical) glass particles conventionally used in slurries are not included in the slurry for manufacturing plug tube sheets according to the present invention. There are differences. This changes the fluidity of the slurry and precludes modification of other process parameters.

The liquidity of the slurry is a function not only of the liquid medium content (e.g. cumol to solids weight ratio) but also of the relative amount of the grinding aid (e.g. hexadecylamine) used in powder tube sheet glass production and the surface water content of the powder particles. It is. It is also a function of the NIL200 percentage in the glass. T
-111 glass has a relatively low Net O, with which it is necessary to use more cumol to obtain adequate cast slurry flow. This in turn tends to cause long cracks on the cylindrical surface of the ceramized tubesheet. Fortunately, however, by exposing the glass powder to "dry" air with a relative humidity of about 3 to 4.5 inches for 1 to 2 hours, it is possible to remove a small amount of surface moisture from the glass powder before turning it into a slurry, thereby improving the workability of the slurry. It is possible to keep the coumol-to-solids ratio low without too much.

It has been found that it is advantageous to limit the mill size during the milling operation to ensure that the majority of the tubesheet has a sufficiently high solids content that it is helium leak tight. 6Kf 20X
20mα At, 1 with o3 cylinder (1 ball #)
, to T-111 glass 7.5 milled in a 5 gallon (5,86 t) mulite grinding pot. The maximum solids/cumol ratio (for adequate slurry fluidity) seen with the batch was 3/1 and only a low percentage of helium-tight tube sheet was produced. 12X12 - 1 coat of 9 in a cylinder 1.2) (0,95t) 0 crushed in a pot
The 15-breast batch reached a 5/1 ratio before it turned into a fine powder and the slurry viscosity became too high. That is, a higher ratio results in a greater proportion of helium-tight tubesheets.

Experiments were conducted using T-1 glass that was crushed using a small crusher.

In this experiment, we were able to examine the effects of the amount of grinding aid used and the solids-to-cumol ratio on helium tightness. The results show that the amount of grinding aid used (grams per glass 1002) is 0.75 to 1.
．． It has been shown that the solids to coumol ratio can range from 4.0 to 5.5 to 1 depending on the amount of grinding aid used. Good results have consistently been found in making plug tube sheets from T-111 glass ground using about 1% hexadecylamine (HDAM') and solids to coumol ratios of 4.5 to 5.4 to 1.

Poor results have been experienced at solids to coumol ratios of 5.5/1 when using only 0.75% CHDAM. ) At least enough HDAM must be used in each case to create one monolayer of HDAM on each powder particle. Usually more is better.

The relative amount of HDAM required to adequately grind relatively soft T-111 glass is substantially greater than that of harder glasses (eg, capillary glass). High-grade removal of HDAM from soft (borate) glass is difficult and this causes bubbles that are clearly seen in diamond cut sections of fired tubesheets (using scanning electron microcasting). Although the bubbles are connected and do not create leakage channels, expansion may occur from their formation (during firing, as described below).

Another problem with glass composition is excessive water content. If the glass is exposed to moisture, or if undesirable moisture acquisition alters the performance of the glass as a component of slurry and/or tubesheets, the glass must be handled in an environment of controlled moisture content. For example, ceria-containing glass was found to be severely degraded in a reduced humidity atmosphere in a so-called "drying chamber" and had to be handled in a glove box under dry nitrogen.

Conversely, as discussed above, a certain minimum water content of the tubesheet (or seal) glass particles may be important to achieve the desired slurry flow properties, at least for some glasses.

The dry composition and thermal properties of a number of representative glasses used as fibers, tubesheets and seals in fiber/tubesheet assemblies and batteries are shown in Table 1.

The best glasses used as seals and/or tube sheet glasses are the ternary glasses listed in the table, T-1,
TI, ■ and ■. See Example 6 and the discussion that follows.

Tube sheets and seals are essentially Na! o/B2O3
/ 3 i Q Togarasuyo Translation Shisono Bt 03 vs. NO
The molar ratio of x0 is preferably in the range of 9 to 24:1. Particularly good is tube sheet glass IhOs vs. 5
iot molar ratio of B, 03 to 5iO in sealing glass
It is preferable that the ratio be approximately equal to the z ratio.

Note 1. Measurements were made on glass samples that had been tempered and annealed.

It is not the same as the Tg of the finished tube sheet, seal or capillary.

Removal of glue (min'M) on isolation tape within fiber bundles also requires high temperatures as does removal of hexadecyl (or other amines) from tubesheets, but sintering can be done at temperatures lower than the temperatures required to oxidize the glue. .Therefore, the difference between phosphoric acid/sintering
Either method can be used.

In both methods, sintering takes place in an aluminum heating block in room temperature air at atmospheric pressure (atmospheric temperature 20-24°C, relative humidity 3-4.
5%).

In a less preferred method, the tubesheet is first dried by heating at a rate of 300°C per hour to 100±5°C and kept at this temperature for 30 minutes. Then 3500± at a rate of 600℃/hour
Heat to 3°C and hold at that temperature for 45 minutes to remove most of the amine. Actual sintering involves heating the tube sheet at a rate of 400°C per hour to 470±1°C, and
It is done on time. It is then cooled at a rate of 300°C per hour or less. The fiber/foil bundle is then placed in a vacuum heating block and heated to 240-260°C for approximately 2 hours.

Additionally, the preferred method of amine removal and agglomerization is performed prior to sintering. The entire dry tubesheet/fiber (and other) assembly is heated in vacuum to 240-260° C. for about 2 hours. The assembly is then cooled and the tubesheet is heated as before to 350°C and sintered at 470°C.

It has been discovered that "foaming" occurs in tubesheets densified by the first method during firing (and/or post-firing heating steps), apparently due to the formation of residual amine bubbles.

This can be done by up to 9 inches expansion of the tubesheet volume.

However, the tubesheet densified by the second method undergoes contraction rather than expansion. This shrinkage may be sufficient to cause longitudinal tension cracks in the fired tubesheet surface if the coumol content of the slurry is relatively high, but this may not be the case.

Both methods are useful for comparison with methods for disk-shaped tubesheets that use vacuum ovens, which require fine temperature control.

To better understand how to incorporate sintered tubesheets into batteries, reference is made to Figure 2, which shows a "two-chamber" plug tubesheet (without electrochemical reactants). The prior art and inventive parts of the battery are shown in FIG. 2 (although the entire battery is new as a combination of old and new parts).

Generally, the battery indicated by number (19) consists of an aluminum anode (or anolyte) tank (20), a cathode (or catholyte) tank (21), and a plug tube sheet (22). (20) and (21)
) and a sealing glass body (23). Tanks (20) and (21) have pre-installed inlets ((24) and (25), respectively) that are open but closed after the tanks are filled with anolyte and catholyte as shown in the figure. . The tank (21) has an internal assembly (generally (26)) which is only slightly shown in the figure but includes a number of hollow glass fibers (27). The fibers extend into the tubesheet (22) and are "planted" in the upper end portion (28).
) and a lower end (29) with a closed tip. The assembly (26) includes a foil aluminum cathode current collector/
There is a central aluminum shaft wrapped with a system distributor mantle (31) and a mantle of aluminum isolation tape (32) thicker than the fiber diameter. To improve the electrical contact between the foil and tape mantle, there are several radial heli-arc beads ((33), only one shown) on the lower part of the wrap. There is).

An aluminum tail (34) is connected to the rolled lower part by one of the weld beads (33). The tail extends and enters the entrance (2
5) is connected at its lower end so as to crease and/or adhere in the metal body created when the inlet (24) and (
(25) also serves as electrical terminals within the completed battery) o The inner assembly is further coated with a wax aluminum tape jacket (25) with twills attached to the adhesive layer when rolled to maintain constant spacing between adjacent fibers (25). 35) (the adhesive is finally decomposed and removed).

FIG. 2A is an enlarged view of the encircled portion of the internal assembly (26). It has a current collector/system distributor foil mantle (31) with adjacent lil fibers and continuous fibers/
The apertures (36) for channeling the catholyte between the foil mantles can be seen more clearly.

FIG. 2B is an enlarged view of the circled area of the anode tank seal from the tubesheet. The lower end of the anode tank (20) is a collar type 1 supply channel (generally (37)), and the lower end is machined thin (for example, 5 mil) and later becomes a seal (23). Pre-glazed (described below).

Bulge at the lower end of the tubesheet in Figure 2 (39)
is made up of the presence of a cotton cord (40) attached (as part (10)) in step E of FIG.

FIG. 3 shows a "single chamber" cell (generally (41)) which differs from the two chamber cell of FIG. 2 in various respects. The battery consists of a fiber bundle wrapped in foil (43) and a plug tube sheet (4).
4), an anode tank (4) with an extending glass seal (45) and an anolyte inlet (47) that serves as the battery anode terminal;
6) It has an internal assembly consisting of: The internal assembly is in a stainless steel casing (49) with a stainless steel isolation cylinder (48), and the casing has a catholyte inlet (50).
) and prefabricated insulating seals (generally (53
) The bottom edge of the lower cylindrical metal part (52) of ) ) is hermetically connected by a welding bead (51). Parts (52)
The upper edge of is hermetically connected to a hard insulating glass ring (54),
It is also sealingly connected to the lower end of the hook-shaped metal body (55). The top end of the bell (55) is sealed around the inlet (47) with a weld bead (56). Insulating seal (53)
The metal parts (52) and (55) are made of KOVAR, a known alloy of iron, nickel and cobalt. The latter insulating seal is sold by Larson Electronic Glass Co., Redwood City, Calif., USA. The electrical connection between the bottom of the part (43) and the casing (49) is made by a thick piece of aluminum foil (57) extending from a terminal (not shown).

The lower part (not numbered) of the casing (49) serves as the catholyte container. The seal between the tubesheet and the anode tank is made by (1) immersing the processed part of the tank supply channel (see Figure 2B) in fused seal glass. .

(2) Remove the processed part while maintaining sufficient gas pressure in the tank so that the adhered glass hangs from the supply channel in the shape of an open cylinder or collar, (3) solidify the collar, and (4) remove it from the inside of the collar. The tubesheet is inserted, (5) the collar (and tubesheet) is heated to comb the collar and contract into an annular shape on the tubesheet surface, and (6) the assembly is slowly cooled.

Generally the method is the same if seals are made on both the anode and cathode tanks (as shown in Figure 2). However, the foil-wrapped fiber bundle and the tubesheet must be placed in a feed channel with a (open-bottomed) cathode tank and glass, respectively, before being lowered onto the tubesheet roll from which the anode tank protrudes. It won't happen. Also, both seals on the bottom of the cathode tank (
It is better not to weld it until after it has been removed (at the same time). Figure 2
As shown in , the glass for sealing becomes a single piece of glass after the sealing operation is completed.

In particular, step (5) is carried out either by induction heating or by simple resistance/conduction heating. The latter is much preferable.

In the induction heating process, the tubesheet and bundle assembly and the immersed anode tank supply channel are made of short cylindrical carbon rings and VYCO
It is placed in a Pyrex tube along with the R support isolation tube.

Place a carbon ring on top of the VYCOR tube and around the supply path. The entire tube and contents were heated under an inert atmosphere in a heating machine for about 4 hours.
After heating to 00°C, it is lowered through an induction coil until the carbon ring is inside the coil. The coil is loaded to heat the ring so that it becomes red hot, and the ring in turn heats the seal glass by radiation.

In the preferred heating method (such as the one-chamber Kameike processing application), the entire anode tank is placed between two halves of a 'split' nickel sleeve shaped to support the tank without interfering with insertion of the tubesheet into the immersion feed channel. The nickel cylinder is slid into a tight-fitting, thick-walled steel inner cylinder that is wrapped with an electric heating band and an external insulation layer.The tubesheet/fiber (etc.) assembly is inserted with a centering jig and the tubesheet is fried in a laboratory jack until it is properly positioned in the glass immersion feed channel.The heating band is loaded and the sealing glass collar is raised to a specified hot water temperature and held there for a specified period of time (this depends on the temperature). (For glass, 15 minutes at 495°C is known to be appropriate.) Then stop heating and allow the whole thing to cool down gently. Remove and separate the broken sleeve and anode/tube sheet/9# (etc.) assembly.

The following examples are for the purpose of illustrating the invention and are not to be construed as limiting in any way inconsistent with the claims.

Example 1 A slurry of 30 y of "hard ceria-1 glass" (see &I) powder ground with Cumol 4.82 and hexadecylamine according to the method of U.S. Pat. No. 3,917,490 is made in a vacuum degassed bottle. 3,800 hollow glass fibers (Table LD-406 glass) each having a length of 6 in. (t15.240), an outer diameter of 80 microns and an inner diameter of 50 microns, closed at one end. were placed in the form of a ladder on a normally released isolating aluminum foil tape (112) with rubber cement (by solvent evaporation).The number of fibers per meter of ladder length was 20.

A 1.9 m long ladder was rolled up with a covering tape and a 4.5 inch (11,43011) wide, 12.7 micron (5 mil) thick air fired molybdenum coated aluminum foil plate approximately 2 m long. The thickness of the isolation tape was such that the spacing between the foil plates and the next mantle was 12.7 microns (5.0 mils). Fiber bundle length 2.5 inches (6,35α
) gently (for 5 minutes) approximately 1.25 inches (3,18cm) into the ultrasonically vibrated slurry.
m) Grated to depth and kept there for about 60 minutes. The resulting "soaked brush" was then pulled out and the excess slurry was squeezed out. 1 cotton string and 1 aluminum wire were attached (Fig. 1 Step E).
Soaked in slurry again. The resulting raw tube sheet was gently dried and placed on a 1.27 m aluminum heating block.
It was inserted into a diameter (black surface) well to a depth of 1 inch (2.54 crn) without touching the wall.

The block was then heated to fC: 100 for 30 minutes.
℃, 400°C for 30 minutes, then 505°C for 1 hour.

After cooling gently, the "fired" tubesheet was trimmed with pliers (all fibers open) to a 0.25 inch (0.64α) tip (including the aluminum ring). The resulting tubesheet/fiber(s) assembly was tested and found to be helium-tight (as previously described).

Example 2 A small (fiber 5
00pcs) Plug tube sheet/fiber (etc.) to attach the assembly to ensure that the helium is tight and also use T-I-ternary 1 glass to seal the tube sheet from the anode tank to a complete one-chamber battery. Incorporated. Example 3 Before admitting the advantage of the Tg balance between the tube sheet and the seal, it is important to note that the battery can be charged/discharged satisfactorily for 8 weeks (at about 300 degrees Celsius) by adding sodium sulfur to the battery. T
- Fifteen helium-tight two-chamber plug tube sheet cells were manufactured using induction heated seals made of either ■ or ACI glass. Of the 8 batteries using T-1 glass seals, 300 yen including sodium and sulfur
I cycled the 'C a total of 14 times and 2 lasted 6 days, none of the other 5 lasted more than 2 days. ACI
Two of the seven batteries made with glass seals lasted for four days (
(10, 11 cycles) and the residue was 3 days or less.

Example 4 When using D-4069 fibers, D-406 tube sheets, and T-111 seals for a large number of batteries in one chamber, a certain level of stability was experienced that was better than the results in Example 3, but after 6 days or more, i.e. 13
Only a few cells lasted up to 12 days (11 cycles), but all cells were helium-tight when tested.

D-4069 fiber, T-I11 tube sheet and T-
Two single-chamber batteries with a nominal capacity of 12 Amp-hours were constructed using IV seals. One lasted only 8 days (10 cycles), and one lasted 31 days (42 cycles) (the molybdenum-coated aluminum cathode foils of both cells were air fired to provide a surface molybdenum oxide layer).

Example 5 A total of 26 one-chamber helium-tight plug tube sheet batteries (nominal capacity 12 amp hours) were manufactured. The fibers of each cell were made from D-406 glass, and the tubesheet and seal were made from the same ternary glass (T-111). The molybdenum coated aluminum cathode foil of the 8 cell was not air fired. The other 18 foils were air fired. 18
The tube sheet glass used in half of the cell was nitrogen purged. This was not the glass used in any of the other groups of batteries. 300℃ for these 26 batteries
The lifespan in is shown in the following table ■.

The variation in life exhibited by the same nominal cells under the same nominal conditions illustrates the inherent difficulty in reproducing hollow fiber cell manufacturing with current technology. However, the benefits of using a highly balanced seal and tubesheet glass and the unbalance that results from a nitrogen purge of only one of the glass, which was thought to be balanced, are still evident from the tabulated results.

Table ■ No PA 4 L on both tubesheet and seal 3138 PAS#410 Low & found PA6#129 Open circuit after cycle 8, low NaPA
9# 378# # #PA
IO# 2120 PA20 # 4839PA29
# 7844PA30 #
1214PA47 159 214 PA48 # 23214PA51
#1312PA53 1 1
820 PA 113 # 128 189
Low NIL, PA 182 ticked at 5 amp hours
#100 126PA183
#3 4 Table■ (Continued) PA185 Yes 125116 Battery heater damaged PA187 #1 2PA118
#3 3 Tube sheet cufflinks N! -/← Digitized PA120 1 402
8 # #PA129 1
1 1 1 #PA13
0 1 0 0 tt
#PA132 1 4 2 1
#PA133 #5
4 # gPA137 1'
1 1 tt tt
PA138 1 1 1 #
#PA142 1 1 1
#ttExample 6 A 6 ampere hour single chamber battery 1 with relatively long life using D-406 fiber, tube sheet and seal glass shown in Table m
Two 12 ampere single chamber electrodes were manufactured.

Table ■ Ternary tube sheet and seal PA279 6 T-I T-1119
6252PA214 12 T-111T-I
V 205 107PA 34 12
Battery PA47 is shown in the table below T-4T-111252116
, PA 113 and PA 185 (Table ■) and PA
279, PA 214 and PA 34 (Null
) Tg and α of the tube sheet and seal glass used
Values and compositions (81 gal) are shown. Table ■ also shows each tube sheet and seal glass. Q3/
The molar ratio of SiO is also shown. The ratio of the latter ratios for each battery is also shown.

It is clear from the examples above that long life is obtained when the glass compositions of the tubesheet and seal are closely matched. The longest life for cells in which both the tubesheet and seal glasses are ternary (sodium borosilicate) glasses is when the B@Os to NIL2O% ratio is in the range 9 to 24 (also Btu/Sin).

The ratio is almost the same for both tube sheet and seal glass)
, that is, preferably 30 to 31.

Although it is highly preferred to produce ceramic powder particles in the presence of a grinding aid (eg hexadecylamine), it is not essential. That is, the amine or equivalent compound can be used after the powder has been produced (such as by crushing the glass without any auxiliaries and sifting out the finer material for use as a powder).
The powder may be mixed with other suitable methods. For example, the powder may be stirred with a solution of the amine in a highly volatile solvent, filtered and dried.

Although it is highly desirable that the ends of the fibers planted in the tubesheet are evenly spaced (or evenly packed), this is not essential. It may vary between cross-sections along the cylindrical axis as well as cross-sections along the cylindrical axis.

Again, it is preferred, but not essential, that the vertical axis of the tubesheet be coextensive with the vertical axis of the bundle of fibers, foils, etc. The tubesheet axis may spread out radially even if the end of the fibers planted in the tubesheet change. Likewise, if the tubesheet axis does not extend co-extensive with the fiber bundle axis, it is at least parallel to it. It is preferable. However, this is not essential; the tubesheet axis may also be inclined relative to the bundle axis.

It is highly preferred, but not essential, that the fiber lengths that are not "bundled" are parallel. The fibers may be oriented eastward in any suitable arrangement, and the free ends of the bundles are collected in a ``brush'' that can be planted in a plug-shaped tube sheet by the method described above in a heavy electric manner and spread out in a vine-like manner. For the purposes of the claims of the present invention, multiple fiber bundles with ends mounted on a common tubesheet are considered to be part of a single "bundle". The bundles are generally U-shaped and the fibers may be open at both ends and terminate within the same (external) surface of a common plug-shaped tubesheet.

Alternatively, the long fibers may be straight, arcuate or generally U-shaped, and may pass through separate two-plug tube sheets at both ends. In this case, the ends of the fibers are usually spaced apart, and the two tube sheets may or may not be made at the same time.

Whenever the ends of the fibers are open, one end of each fiber is filled, for example with wax that can be removed later, to ensure that the slurry does not penetrate deeply into the unbroken fibers during the first planting (soaking or other) operation. It will be recognized that it is necessary to take some measures to replant the other end of the fiber. It will also be clear that the part of the fiber that is "soaked" in the slurry need not be open; for example, the closed end may be removed from the unplanted end before fiber laying begins. After firing, the ends of the composite tubesheet/fiber structure can be cut open (of course this requires firing treatment by known methods to plug off unsuitable fibers) and the anode tank. The shape of the bottom of the tank between the wall and the feed channel that fits into the tubesheet is preferably conical, as shown in FIGS. 2 and 3, but this is not necessarily an option.

In all embodiments of the invention, the ratio of the average effective diameter of the unplanted portion of the fiber bundle to the average effective diameter of the planted portion is equal to or Please understand that it varies within approximately +V.

[Brief explanation of drawings]

FIG. 1 is a vertical perspective view of successive steps (A through J) of the preferred method of manufacturing hollow fiber etc./tubesheet assemblies of the present invention. FIG. 2 is a vertical cross-sectional view of a two-chamber sodium/sulfur cell incorporating the hollow fiber/tubesheet assembly of the present invention. FIG. 3 is a vertical cross-sectional view of a one-chamber IJum/sulfur cell incorporating the hollow rim cone/tube sheet assembly of the present invention. Number in the diagram 1 Assembly 2 Aluminum tube shaft 4 Hollow fiber 5 Brush 6 Slurry 17 Chemical tube sheet 20.46 Anode tank 21 Cathode tank 22.44 Plug tube sheet 49 Cathode casing □% Applicant: The Dow Chemical Company 2r
...) Agent Patent Attorney Takehiko Saito '2' 〃 〃 Ryoji Yosera 1 Pa'-'' GFIG, I 'FIG, 3 Procedural amendment (method) % formula % 1. Indication of case 1985 Patent Application No. 37553 No. 2, Name of the invention Elongated tube sheet for hollow fiber type batteries and its manufacturing method 3. Relationship with the case of the person making the amendment Patent applicant name The Dow Chemical Company Name Patent attorney
(7175) Takehiko Saito', ゛-゛ 15, Date of amendment order ゛...April 22, 1986 6, Column 7 for brief explanation of drawings of the specification subject to amendment, Contents of amendment

Claims (1)

Claims: 1. Spaced ceramic hollows whose ends are closely packed together and embedded in a generally cylindrical body made of a viscous slurry of ceramic powder material in a volatile liquid. consisting of a bundle of lengths of fibers, the unembedded portions of said fibers forming the larger diameter portion of said bundle, and the average spacing of adjacent embedded fiber portions being equal to the distance between adjacent fibers forming the larger diameter portion of said bundle. the average spacing of the sections is less than 1/2, and the slurry is transformable by drying, heating and cooling into a solid ceramic tube sheet with which the embedded fibrous sections are in sealing connection therewith. 1. A hollow fiber bundle comprising a composite structure including the embedded portions and the embedded portions. 2. The ceramic powder material has a molar ratio of 1.0/9.0/
Na_ in the range of 0.3 to 1.0/24.0/0.8
The fiber bundle according to claim 1, comprising 2O, B_2O_3 and SiO_2. 3. The solid to liquid weight ratio in the slurry is 4.5 to 5.
．． 4 to 1, the liquid is cumene, and the slurry contains hexadecylamine in an amount sufficient to form a monolayer of hexadecylamine on the particles making up the powder. The fiber bundle according to item 1 or 2. 4. The fiber bundle of claim 3, wherein the weight of said amine in the slurry is about 1% of the weight of said powder in the slurry. 5. The above fiber lengths have a molar ratio of 1.0/2.0/0.
Na_2O, B_2O_3, Si in the ratio of 2/0.16
A fiber bundle according to any one of claims 1 to 4, which is manufactured from a glass consisting of O_2 and NaCl. 6. The fiber bundle according to any one of claims 1 to 4, wherein the fiber length and the tube sheet are made of the same ceramic material. 7. Apply the slurry to the open-end embedded part of the fibers.
Any end portion of the fiber that is unsuitable is injected to a substantially greater extent, the cylinder is so altered, and the end portion of the resulting composite structure is removed. and the length of the removed portion is such that it contains the tubesheet material within the lumen of the suitable fibers but does not occlude the unsuitable fibers. The fiber bundle described in any of the above. 8. A hollow fiber bundle consisting of a helium-tight internal assembly consisting of a single generally cylindrical ceramic tube sheet and an anode tank in sealing connection with said tube sheet, said hollow fiber bundle being tightly packed together at the ends. a plurality of spaced apart lengths of ceramic hollow fibers embedded in and in intimate connection with said tubesheet, the portions of said fiber lengths not embedded in said tubesheet being suspended therefrom; All of them are closed at the tips, and the embedded sections with suitable fiber lengths are open-ended, and the embedded sections with unsuitable fiber lengths form a tube sheet. The same ceramic material is closed together, the unembedded portion of the appropriate fiber length constitutes the large diameter portion of the bundle, and the average spacing of adjacent embedded fiber portions is less than one-half the average spacing of adjacent non-embedded fiber portions of the large diameter portion of the bundle, the anode tank having a feed channel consisting of a thin-walled collar to which the end of the tubesheet is attached; A high-temperature battery, characterized in that the collar and tubesheet are each inserted and hermetically connected by the same generally sleeve-shaped ceramic seal. 9. The battery according to claim 8, wherein the length to diameter ratio of the tube sheet is within the range of 3 to 6. 10. The glass transition temperature of the seal and tube sheet is approximately 5
They do not differ by more than ℃ and their linear expansion coefficients are approximately 10×10
The battery according to claim 8 or 9, which does not differ by more than ^-^7/°C. 11. Each glass of tube sheet and seal is Ni_2O
, B_2O_3 and SiO_2 glass and B
Claims 8, 9 or 10, wherein the _2O_3 to Na_2O ratio is in the range of 9 to 24:1 and the B_2O_3 to SiO_2 ratio is approximately the same in both the seal and tubesheet glasses. battery. 12. B_2O_ of both glass of seal and tube sheet
12. The battery according to claim 11, wherein the molar ratio of 3 to SiO_2 is 30 to 31. 13. Fiber length is Na_2O, B_2O_3, SiO_2
and NaCl, approximately 1.0/2.0/0, respectively.
．． A battery according to any one of claims 8 to 12, having a molar ratio of 2/0.16. 14. Fiber length is Na_2O, B_2O_3, SiO_2
and NaCl, approximately 1.0/2.0/0, respectively.
．． 14. A battery according to claim 13 having a molar ratio of 5/0.16. 15. forming a plurality of spaced lengths of ceramic hollow fibers into bundles whose ends constitute brushes, producing a slurry of powdered ceramic material in a liquid, dipping said brushes in said slurry, and forming a dipping brush; is compressed to a small diameter, and the diameter of the dipped brush is reduced to such an extent that the average spacing of its adjacent fiber end portions is less than 1/2 of the average spacing of the fiber lengths of the unsoaked portions of the bundle. , allowing the slurry to flow by capillary attraction into any of the open fiber end sections, and drying and heating the object to transform it into a solid ceramic tube sheet, and sealingly connecting the embedded end section therethrough. A method for manufacturing a helium-tight composite hollow fiber/plug-shaped tube sheet structure useful in high-temperature batteries, comprising the steps of: forming a helium-tight composite structure with the embedded end portions. . 16. The method of claim 15, wherein the dipping and diameter reduction are performed while the fiber bundle is rotated about its longitudinal axis and subjected to vibration. 17. A method as claimed in claim 15 or claim 16, including the step of applying at least one wrapping material around the dipped brush to effect said compaction. 18. A method according to claim 17, including the step of partially drying the brush with the dip coating material and then dipping it in the same or a different slurry and applying an outer layer of the slurry thereon. 19. Remove the distal portion of the structure, the length of the removed portion being such that it contains the tubesheet material in the lumen of the appropriate fibers, but not such that it will unclog the unsuitable fibers. A method according to any one of claims 15 to 18.