DK141977B - Method and apparatus for making sheath plates for accumulators and batteries. - Google Patents

Description

(tt (H) PREFERRED EMBODIMENT 1 ^ 1977 DENMARK is not int.ci.s η οι μ / οι «(21) Application No ^ 717/75 (22) Filed on 20 Oct 1975 (23) Lfbedag 20 Oct 1975 (44) The entity appeared and issued a letter to the OJUX I I DIRECTORATE OF THE PATENT AND TRADEMARKET (30) Fri.

Oct 18 1974, 45241/74, GB

23 * dec. 1974, 555ΟΟ / 74, GB

Oct 15 1975 »42226/75, GB

Oct 15 1975, 42227/75, GB

(71) CHLORIDE GROUP LIMITED, 52, Gros venor Gardens, London SW1W OAU., GB.

(72) Inventor: Stanley Charles Foulkes, 12 Cambourne Drive, Deane, Bolton, Lancashire, GB.

(74) Plenipotentiary in blessed treatment:

The engineering firm Lehmann & Ree.

(64) Method and apparatus for producing cover plates for batteries and batteries.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of producing sheath plates for accumulators and batteries by introducing an active material composition containing liquids into the porous sheath of the plate when the sheath is mounted on the conductive element of the plate. The invention further relates to an apparatus for carrying out the method.

Tubular plates may have a variety of different types of tubular material and tubular shapes and may have tubes connected to each other or shaped as separate tubes disposed separately on the pins.

An example of such separate pipe arrangements employing woven fabric tubes has a thin outer plastic sheath provided with perforations having a diameter of 1-2 mm at a spacing of approx.

1-2 mm. The plastic sheath is approx. o, l to o, 2 mm thick.

However, the invention will be described with particular reference to pipe arrangements, where the pipes are a single pre-formed unit, as this facilitates assembly of the pipes on the pins of the plate.

A conventional method of making tubular sheets includes impregnating fabric tubes with a resin to make them rigid, but still permeable, placing the tubes on a system of lead alloy pins, a pin for each tube, and filling the space between the interior of the tubes and the active material pins, e.g. lead oxide powder from a hopper and shaking the assembly to compress the powder into the tube. This process presents significant problems including lead oxide wastage, filling weight disparity, and unevenness of filling, the active material tending to become too tightly packed at the bottom of the tubes during filling but being the top of the tubes below the use.

A proposal under British Patent Specification No. 947,796 to reduce these problems is to extrude an active material paste containing a water-soluble thickener into the high pressure tubes. However, this method results in plates having unpredictably variable electrical performance. There is also a tendency for the paste to decompose and lose its fluidity under pressure and also to assume solid form within the machinery if there are intervals or delays in the production process.

Another proposal according to German Patent Specification No. 2,243,377 is to inject a metered volume corresponding to the inner volume of the tubular plate of an acidic car accumulator paste into the pipes within a very short period of time, e.g. less than 1.5 seconds. The paste is added to a certain amount of additional water. This is said to form a suspension, but in reality this mixture is a thick paste which does not smooth itself. The pastes listed contain 3 parts gray lead oxide, 1 part red lead oxide, 2.96 parts by weight of oxides for each part by weight of acid and water and 0.06 parts by weight of sulfuric acid of density 1.4 for each part by weight of oxide, i.e. 12.6% of the gray lead oxide was sulfated. Said description indicates that the pastes have dynamic viscosities in the range of 3.ooo to 4.ooo centipoises. There is no indication of the method to be used for measuring viscosity or of the measuring apparatus.

The viscosity of the above paste described in German Patent Specification No. 2,243,377 has been measured on a rotary vane viscometer as described below using the measurement technique also described below.

It has been found that this paste has a torque value (as defined below) on viscosimeter with rotary vane of 1.05 Nm.

3 141977

The paste is not self-leveling, ie. when a mass is deposited as a lump on a flat surface, it does not assume a level level surface within a period of 24 hours, although small amounts of liquid are separated from the solid parts during that time.

The process has the disadvantages of requiring accurate measurement of the volume of paste to be injected and the paste is so viscous that it must be pressed into the tubes under high pressure.

A similar method to the above is known from German Publication No. 2.25o.748, wherein lead plates for lead accumulators are filled with a paste-shaped active mass by means of a cylinder with a filling opening, through which the paste-shaped mass, due to gravity, decreases. in the free cylinder compartment. With a piston, the mass is compressed against a sliding valve which is then opened, whereby the mass is pushed into the tube plates during the movement of the piston.

Said need to use a high pressure causes variation of the density of the paste along the tubes as the paste tends to become too compressed at the inlets of the tubes which are bottom of the tubes during use. Furthermore, it causes difficulties in causing the paste to travel throughout the length of a tube, especially in a deep plate. This significantly limits the size of plate that can be filled. This introduces further problems in making accumulators of the paste and using the accumulators.

The object of the invention is to reduce the above problems separately and jointly by using a substantially different method and active material composition.

It is peculiar to the process according to the invention that the active material in the composition is introduced into the casing as an aqueous slurry comprising an active lead-acid material composition or a convertible material thereof having a torque value measured on a rotary vane viscometer of less than ο, οοδί Nm at 2o ° C, which aqueous sludge is introduced into the casing at a pressure less than 34.3 kPa until the casing is filled with the composition, liquid exiting through the casing walls and allowing the pressure to rise to a value above 34.3 kPa, but not above 686 kPa, after which the pressure is relieved.

Surprisingly, it has been found that by using the method of the invention for filling casing plates for accumulators, an active material sludge having a viscosity as indicated which is far less than previously used can be used to prepare accumulator sheets whose composition is very uniform from top to bottom, ie layered to a very low degree and having easily controllable properties, such as density, ratio of active ingredients, weight of active ingredients, and more. By adjusting the value at which the back pressure is allowed to rise, the degree of consolidation can be varied as desired while maintaining the very uniform consolidation mentioned.

In a preferred embodiment of the method according to the invention, the sheath is arranged in a substantially vertical plane so that solids can settle on the bottom of the sheath under the influence of gravity and that the aqueous mud has a ratio of active material to water in the region. , 4: 1 to 2.5: 1, by weight, the material of the jacket being selected to filter out active material while allowing the passage of liquids, at least partially retaining the solids in the jacket, and the liquids in at least partially passing out through the casing walls.

The term sheath covers systems of separate tubes as well as systems of tubes interconnected or formed of sheets of material in addition to covering any sheath capable of forming a pouch or pocket around the current carrying element (s) of the plate and capable of filtering active material as a layer around the conductive element (s).

For ease of description, the method will be described essentially with reference to tubular plates.

The ratio of the sludge volume introduced into the tubes to the total internal free volume of the tubes in the sheet is preferably at least 2: 1 and preferably at least 3: 1, 4: 1 or 5: 1, preferably 5: 1 to 15: 1 or most preferably 6: 1 to l0: l, as these values have been shown to give the optimal results.

The internal free volume of the pipes is the volume within the inner diameter of the pipes which is not occupied by the conductive elements.

The aqueous mud comprises a mixture of water and particulate active material. There is possibly no acid added to the sludge and the sludge may be substantially free of sulfate.

The weight ratio of solids to liquids in the sludge within the range defined above depends on the particular active material used and the permeability of the pipes being filled.

Preferably, the aqueous mud comprises a mixture of particulate active material, e.g. lead oxide, and water in a weight ratio in the range o: 5: 1 to 1.5: 1 or 2, o: 1, preferably 1: 1 to 1.8: 1 or approx. 1.5: 1, as these values have been found to give the optimal results.

A sludge having an oxide ratio of o: 1: 1 had a density of 3 o 1.1 g / cm; o, 5: 1 a density of 1.4; 1: 1 a density of 1.7; 3 1.5: 1 a density of 2.15 and 2, o: l a density of 2.35 gr./cm.

5 141977 3

The sludge preferably has a density less than 2.5 grams / cm.

The solid particles in the sludge were such that less than 1% by weight was above 20 microns and less than 1% were below ο, οοί microns, and 95% by weight was less than 5 microns. These particle sizes were determined by sieving.

With the non-woven fabric described below, it is preferred to use sludge without acid additives having a ratio of solids to liquids of 2, 0: 1 to 5, 5: 1, e.g. 1.5: 1 to o, 7: 1, these areas being the optimum ones which have been shown to give the best results.

Especially with sludge without acid additives, it is preferred to use sludge frame compositions containing gray lead oxide or red lead oxide or mixtures of gray and red lead oxide containing up to 7% red lead oxide and preferably mixtures of gray lead oxide and red lead oxide in a ratio by weight of 66:34 to 33:67.

With the spun-woven fabric described below, the best results are obtained by using sludge without acid additives with a ratio of solids to liquids of 2.5: 1 to 1: 1.

With the woven fabric described below, it is preferred to use sludge without acid additives with a ratio of solids to liquids greater than 2, 0: 1, e.g. in the range of 2.4: 1 to 2.5: 1.

The slurries useful in accordance with the present invention have viscosities of substantially the same size as water, i.e., small compared to conventional accumulator pastes and the pastes proposed in German Patent Specification No. 2,243,377. The viscosities of the sludges of the present invention cannot be measured with a Brookfield viscometer because the solids stand out on standing.

Sludge scans useful in the present invention are readily flowable and the solids settle rapidly from the liquid phase, namely in less than 15 minutes upon standing.

As mentioned, the compositions are characterized by having a torque value (as defined later) measured on a viscometer with rotary vane of less than o, oo81 Nm, preferably not more than o, oo54 Nm at 20 ° C.

The suspension half-life (as defined later) of the sludge is preferably not more than 15 minutes, preferably in the range of 1 to 10 minutes.

The slurries have viscosities which are essentially independent of shear rate, i.e. they are not thixotropic gels, and although the viscosities decrease with an increase in shear rate, this decrease is not pronounced and a gel does not form when the shear force is removed.

6 141977

The sludge may contain usual fillers and additives to the active material, such as hydrophobic or hydrophilic silica, e.g. o, 1% to o, 5% by weight based on the oxide.

In one arrangement, the tubes are allowed to fill substantially under the influence of gravity and the pressure is then allowed to build up to exert pressure on the active material in the filled tube for only a fraction of the time it takes to fill the tube. Thus, the pressure according to the invention may be in the range of 34.3 to 343, preferably 68.6 to 206 kPa, and applied in e.g. one-tenth to one-half of the time it takes to fill the tube, or at a time equal to the time it takes to fill the tube. Thus, it can take 5-15 seconds to fill the tube and the pressure can be applied for 1-5 seconds. It is possible to control the final filling weight of the plate by the specified build-up of the pressure.

In another arrangement, the pressure is applied over a longer period of time. In this arrangement, the tubes are substantially filled with gravity under the influence of gravity, which is pumped into the tubes under a zero pressure, and when the tubes have been filled, the pumping is continued and the back pressure allowed to build up to a value not exceeding 48o kPa. . Thus, the pressure may be in the range of 34.3 to 343, e.g.

68.6 to 206 kPa. The weight of the oxide in the tubes can be adjusted by adjusting the pressure built up, as indicated in the examples. Usually the pressure is only allowed to build up to the set value at which point the pressure is relieved.

Surprisingly, and contrary to the previous proposals, where the entire filling operation is carried out under high pressure, resulting in the active material being layered, with the paste closer to the entrance, this arrangement allows the density of the active material in the tube to increase evenly. throughout the tube, with no layer formation.

The material of the tube is selected as indicated above so that it has a filter effect on the active material used. However, this does not mean that all the active material is removed from the fluids flowing out of the tubes, but merely that a portion is retained in the tubes.

As mentioned above, the ratio of active material to liquids to be used depends on a variety of factors including the nature of the material from which the tubes are made.

A balance must be found between the need for the material to have a high water permeability to achieve good conductivity during use in the accumulator and the need for the material to have a good filter effect so as to allow the filling to be carried out quickly and the active material retained in the tubes. over long periods of use and under shock and vibration conditions. A suitable material is obtained from a nonwoven polyester fiber sheet which is o, 5 to o, 7 mm thick and weighs 12o-16o gr. square meters. This is not perforated since its porosity is derived from the various interstices between the fibers from which it is made. It has a nitrogen permeability 2 (as defined later) of 8.0 liters / cm / min. and a water permeability (as defined later) of 1.5 liters / cm / min. This material has proved suitable for the manufacture of the jacket.

More generally, it is preferred to use a material having a nitrogen permeability in the range of 0.5 to 20, preferably 1 to 10, or more preferably 3 to 9 liters / cm / min. Preferably, it should also have a water permeability of at least o, ol liters / cm / min, preferably 0.1 or o, 5-1, 2 or 5 liters per liter. minute or more.

As indicated below, it is preferred to use a sludge composition wherein the active material particles have a mean particle size in the range of 5 to 20 microns.

However, medium particle size material in the range of 1-3 ° or 50 ° or 100 microns can be used equally well as long as the tubular material still has sufficient filtration effect. Higher particle size active material such as granulated material, e.g. with a particle size of 0.1 to 1.0 mm can be used and, if desired, mixtures of active material of different particle size can be used.

The active material may be any desired material for the accumulator concerned, and although the invention is described with reference to lead-acid accumulators, the invention may teach the necessary requirements for the active material composition and the shell material, thereby obtaining filtration filling. and a layer of active material builds up from the bottom of the jacket (the upper one during use), applied to other electrochemical systems.

Referring again to lead acid systems, the lead oxide preferably has substantially all of its particle size particles less than 10 microns, e.g. less than 1% by weight is over 2 microns in diameter. Furthermore, less than 1% is less than ο, οοί micron in diameter. Typically, at least 5%, e.g. 95% by weight is less than 5 microns, 5% by weight is less than 100 microns, and 5% is less than 1 micron. The oxide may comprise a mixture of medium lead gray particle size 2 microns and red lead particle size 5-10 microns. The ratio of gray to red lead may be in the range of 95: 5 to 5:95, although 9o: lO to 3o: 7o, e.g. 33:67, is preferred.

The apparatus for carrying out the method according to the invention comprises at least one filling station, wherein the plate is winch-supported with its sheath mounted on its current conducting element in a substantially vertical plane, and a filling manifold disposed next to the upper part of the supporting means, and a sludge storage tank provided with stirring means for holding the active material in the storage tank in suspension as a slurry, and the apparatus is characterized in that delivery means are connected between the storage tank and each filling station to deliver the sludge from the storage tank to the manifold at a selected filling station, that means are positioned below the filling station for collecting the fluids exiting through the walls of the sheaths, the delivery means includes recycling means for recycling the sludge to the storage tank when the sludge is not delivered to a filling station, the filling station has a frame rigidly attached to the filling manifold and are top and bottom clamps arranged to releasably clamp the plate to the frame, and that the manifold has a spout nozzle unit consisting of rigid feeder spacers spaced in a straight line with their centers on the centers of the plate tube and with outside diameters corresponding to to the inner diameters of the plate tube.

According to the invention, the manifolds for the manifold may comprise a pump having an inlet pipe communicating with the storage tank and valve means, the recirculation valve communicating with the discharge of the pump to conduct, preferably selectively, the sludge from the pump outlet to the filling station, or if more is used. than a station for a selected station or for recycling the sludge to the storage tank.

The clamps may be toothed and have the same shape as the exterior surface profile of the bottom and top of the tubular plate.

X preferably the smallest clamp is provided with an elastic sealing liner.

The guide tubes can extend through an elastic gasket, the dimensions of the frame relative to the plate being such that the end of the plate must be pressed into the gasket to place the plate in the supporting members.

Preferably, a pressure-sensitive valve is disposed in connection with the inlet side of each filling manifold.

Preferably, there are at least two filling stations for each pump and sludge storage tank, and the recirculation valve is a three-way valve.

The pressure-sensitive valve or each may be adapted to activate automatic switching of the recirculation valve or valve means connecting the manifold or each manifold with the common feeder tube to the recirculation position and to relieve the pressure in the supply line to the plate as soon as a preset pressure is reached.

The process of the invention is not limited to filling tubular casing sheets. Thus, other sheath shapes can be used, e.g. casing-shaped sheaths, and in this case the grid no longer needs to be in the form of a cam of pins, but may be a usual molded grid or a grid-shaped plate, e.g. an expanded metal mesh or plate with openings punched through it, and it can also be a solid plate as long as the necessary current gathering function is sufficiently performed.

The sheath may be of flexible material or of rigid material, but at least when the sheath is flexible, it is preferable to support its sides with porous support members, e.g. stiffened with small holes, plates, nets or grids during the filling operation so as to hold the plate with substantially parallel sides while allowing the fluids to pass through.

> With this arrangement, the access manifold must also be modified so that instead of a series of tubes inserted at the ends of the individual tubes of the casing, a single or double tubular slot is provided for insertion into the open bottom of the casing. A double slit arrangement placed over the end of the grating and forming a pair of slots extending along each side of the grating and can be clamped thereto may have advantages over a single slit arrangement.

The end of the sheath can be sealed with an elongated base bar after filling. This may consist of an inner plug which grips the end of the grating and an outer clamp or flange on the plug which is adapted to grip the outside of the casing and hold it against the plug.

In another alternative embodiment, instead of an inlet manifold of fixed tubular outlets or solid slots, an arrangement of retractable filler pipes extending down the casing may be used. The arrangement will start with the filler pipes fully extended »into the casing around the pegs (which now need not have centering ribs as the filler pipes perform this function).

As the active material exits from the ends of the tubes, these are retracted up along the casing and finally halted at the open upper end of the casing, where they can be momentarily clamped and then released to complete the filling of the sheet.

However, this arrangement is obviously more complicated than the arrangement where the sludge is simply introduced at the upper ends of the tubes, and this simple arrangement is therefore much preferred.

ft lo 141977

The invention will now be explained in more detail with reference to the drawing, in which fig. 1 is a schematic side view of an embodiment of the apparatus according to the invention; FIG. 2 is an enlarged schematic perspective view of the filling box shown in FIG. 1, FIG. 3 is a schematic view of a portion of the lower terminal shown in FIG. 2 in the open position, with only some of the tubes of the plate shown; FIG. 4 is a cross-sectional view taken along line IV-IV of FIG. 3, FIG. 5 is a partial cross-sectional view of a portion of the upper terminal in the open position, as in FIG. 3,. FIG. 6 is a front elevational view of the rotary vane viscosimeter used to measure the viscosities of the slurries used in accordance with the invention; FIG. 7 is a front elevational view of the vane assembly of the viscosimeter of FIG. 6, FIG. 8 is a plan view of the container for use with the viscometer of FIG. 6 to contain the sample whose viscosity is to be measured; FIG. Fig. 9 is a plan view made from an optical photomicrograph of the nonwoven fabric described below and used in the examples; Fig. 10 is a front view of a preferred embodiment of a satellite refill station for use in a modification of the invention, a central sludge preparation station delivers sludge to a number of satellite filling stations; fig.11 the satellite filling station of fig. 1, the satellite filling station of FIG. lo set ^ from above ^^ s' * I1 141977 fig. 13, in connection with FIG. 1a from the central sludge preparation station seen from above, fig. 14 the station of FIG. 13 is a side view of FIG. 15 is a front view of a preferred embodiment of a filling manifold and the upper terminal scan used in the filling station shown in FIG. 1, FIG. 16 is a plan view of the filling manifold shown in FIG. 15, FIG. 17 is a cross section along line XVXI-XVII of FIG. 15, FIG. 18 is a front view of a preferred embodiment of the lower terminal, scan is used in the filling station shown in FIG. 1, and FIG. 19 is a vertical cross section along the line XIX-XIX of FIG. 18. The apparatus shown in FIG. 1 consists of a sludge tank 1o, in which the sludge to be filled in the plate tubes is stored. The tank is equipped with a vane 11 which is located at the bottom of the tank and is driven by a belt and pulley drive 12 by a variable speed motor 13. A vertical feeder tube 15 extends upwardly immediately above the vane 11 to the inlet of a supply pump 16, also driven by a belt and pulley drive 17 from a variable speed motor 18. The exit from the pump 16 is cursed vertically downwards by means of a supply pipe 19 with a plate filling station 20. The supply pipe continues over a pressure gauge 22, a two-way valve 23 and a fish tail manifold 24. The valve 23 either allows the sludge to flow vertically down to the station 20 or can be set to direct the sludge to the tank 1o over a recirculation pipe 26 extending downward to the immediate bucket. 11. The pipes 15 and 26 preferably have the same cross-sectional area.

The mass of the sludge supply is preferably kept at approx. 15o kg or more generally between loo and 2oo kg, and the sludge mass is introduced into each tubular plate, the individual filling guard being of the order of 4oo-looo gr. More generally, the weight ratio of the active material is e.g. 75 kg in the continuously mixed sludge supply and the individual filling weight located in the range of 20: 1 to 25: 1, e.g.

16o: l to loo: l.

The station 20 has a frame 29 which is rigidly attached to the manifold 24 and carries top and bottom terminals 3o and 31.

Terminals 30 and 31 are toothed and in accordance with the outer surface profile of the bottom and top of the tubular plate, as the plate is inserted into the terminals with its open bottom facing towards the manifold 24. The manifold has a discharge nozzle unit of 6.4 mm long copper or other rigid feed pipes with outside diameters corresponding to the inner diameters of the plate pipes and spaced apart in a straight line, the centers of the feed pipes being located on the centers of the plate tubes.

Thus, the open ends of the plate tubes fit tightly over the feeder tubes and are clamped thereto by the top clamp 30 which may be provided with an elastic sealing liner.

The lower clamp 31 holds the plate in place and presses the tubes against a thickened end section on the pins. The sides of the plate are completely free.

The pins are of the usual lead alloy composition and of the usual: pitching, being mounted on a top bar at centers corresponding to the centers of the tubes, along with which they are to be used. They are preferably provided with short axial ribs which are used to center the pins in the tubes and to prevent the pins from distorting during handling prior to filling.

Station 20 will now be described in more detail with reference to FIG. 2-5.

As mentioned above, the station 20 has a frame 29 rigidly attached to the manifold 24. This frame is hinged relative to each other along the left side edge, and it is the portion 33 which is rigidly attached to the manifold 24. The top and bottom clamps are each in two parts 3oA and 3oB and 31A and 31B. 3oA and 31A are disposed on the movable portion 32 of the frame, and 3oB and 31B are disposed on the fixed portion 33 of the frame 29.

The fixed portion 33 also carries top and bottom locking levers 36 and 37 which are adapted to engage with top and bottom handles 38 and 39 on the movable frame member 32 and the lock loading station in the closed position.

The fixed portion 33 of the frame 29 also carries a bottom support rod 42 which has an opening 43 through which the patch 44 of a plate 45 can pass and which helps to set the plate in the correct position at the filling station.

The top and bottom clamps 30 and 31 have toothed profiles which correspond to the outer cutting dimensions of the plate, and the two parts of each clamp define, in closed position, a series of cylindrical holes 48 which are connected to slots 49 which are twice the the thickness of the fabric 47 in the sheath so as to prevent the sheath from being cut by the clamps.

The bottom clamp 31 presses the fabric 47 in the jacket against the extended shoulders 51 on the pins 52 of the plate to ensure a tight closure. (See fig.

3 and 4).

FIG. 5 shows the clamping arrangement at the manifold 24.

A manifold plate 54 has a series of feeder tubes 55 which pass down through it and have narrowed ends 56 extending through openings in a rubber gasket 58. It is elastic in that it is compressible by the finger pressure to only about 10 inches. half of its uncompressed thickness, which is approx. 3.2 mm thick. FIG. 5 shows the sheath 47 in position over the ends 56 of the feeder tubes. However, the arrangement is in fact designed such that the packer 58 is to be compressed by approx. 1.6 mm of the sheath 47 which is pressed into it to get the top bar of the plate up onto the base bar 42 of the frame (this compression is not shown in the drawing). The clip 3o presses the fabric 47 into the casing around the ends 56 of the feeder tubes 55 to obtain a good seal at the top. The tubes are thus filled while being vertical with their top bar at the bottom.

The pump 16 is one which provides smooth delivery and is of the well-known type, such as that sold under the trade name MONOPOMP, which has a single start screw rotor which fits in a cylinder in the form of a double start screw line with the double pitch of the pitch of the rotor, with the rotor rotating about its own axis in one direction, while its axis orbits the axis of the cylinder in the opposite direction at the same speed. This pump form provides a positive displacement with uniform flow and prevents the separation of fluids and solids in the sludge.

In another arrangement (not shown), the filling station 20 is configured as a double manifold arrangement where each manifold is supplied from the pump 16. The two way valve 23 is replaced by a three way valve and each conduit from the valve 23 to a manifold contains a pressure sensitive valve.

This valve is preferably a pressure relief valve which can be set 2 to any desired pressure, e.g. l, o5 kg / can, and 2 when this pressure is reached, it will maintain the pressure of l, o5 kg / cm until activated, e.g. manually.

The method will then be to insert a plate into a manifold and the valve 23 is switched either from recycling or from the other manifold. The plate is filled e.g. in 5 seconds and then the pressure 2 will rise to 1.5 oz / cm and held there for 5 seconds. During this time, the operator will have removed the filled plate from the second manifold and inserted a new plate. He can then switch valve 23 either to recycle transiently or immediately to fill the new plate.

In an alternative arrangement, the pressure relief valve is arranged to switch the pump supply for recycling and release the pressure on the plate as soon as the preset pressure is reached.

During operation, the filling process is performed as follows.

The slurry is prepared with the desired composition in the tank 1o using the bucket 11. A tubular plate 5o is assembled, the nonwoven fabric tubes 47 being applied to the metal pins 52 and placed 14 to the terminals 3oB and 31B of the station · 2o with its open bottom ends pressed up against the seal 58 and over the ends 56 of the feed tubes 55 on the manifold 24. The portion 32 of the frame is then pivoted to the closed position against the portion 33, and the clamps 3o and 31 are thus closed, and the locking arms 36 and 37 are secured over the handles 38 and 39. The vane 11 is kept in operation and the valve 23 is rotated to the recirculation position, where the pump 16 is connected to the pipe 26 and the pump 16 is started. Recycling continues until the flow is stable. Pressure indicator 22 indicates zero pressure while recirculation is taking place.

The valve 23 is then switched to connect the pump 16 to the manifold 24. The sludge passes down through the station 20, with some of the active material settling in the interior of the tubes, while excess liquid and active material run away through the fabric 47 of the tubes and back to the tank laughed. The valve 23 is held in this position until the tubes have been filled with active material, at which point the pressure indicator indicates a relatively sudden pressure increase. The valve 23 is then switched to recycle the sludge to the tank 1o over the pipe 26.

Terminals 30 and 31 are then opened and the filled plate removed and further operations in the process, such as bottom bar insertion, cleaning, drying and electrolytic propagation, are performed on the plate.

The excess sludge in the manifold 24 falls into the tank 1o.

During continuous operation, the pressure rise indicated on the indicator 22 can be used to control the filling cycle, e.g. for activating the valve 23 and opening the terminals 30 and 31 to release them from the manifold 24 and again engage with a new plate in the clamped position. End switches can be arranged to be actuated by the new plate which engages the manifold 24 to switch valve 23 back to the filling position.

In the modification shown in FIG. lo-19 becomes two or more, e.g. three, satellite filling arrangements as shown in FIG. 1-5 provided with sludge from a central sludge reservoir and cooking tank which is placed on a weight so that it can be weighed continuously. The reservoir is continuously stirred and is provided with a float-controlled water supply so as to keep the volume of sludge constant. The sludge begins with an oxide to water ratio of 1.5: 1. Each satellite refill arrangement is fed to sludge using a variable speed pump. When the weight of the reservoir has dropped by 544 kg and the ratio of oxide to water has dropped to 1.2: 1, the pumps for the satellites are switched off. 363 kg of red oxide and 181 kg of gray oxide are added. The ratio of oxide to water in the satellites falls to approx. 1: 1 while doing this. When the supply from the reservoir to the satellites resumes, the solid-liquid ratio is restored.

In this arrangement, it is preferred to increase the volume of the tank 1o in the satellite refill arrangement so that when the supply from the main tank is interrupted during the refill, the ratio of oxide to water does not decrease too much. Thus, the sludge mass is preferably in the range of 5oo-625 kg, and the weight ratio of the active material in the sludge to the individual filling weight (e.g. 2oo-12oo gr) is thus in the range 13oo: 1 to 2oo: 1, e.g. looo: l to 25o: l. The mixing of the sludge continues in the reservoir during the oxide addition and when this is completed, the pumps to the satellites are reconnected.

The central sludge preparation station 10 is shown in FIG. 13 and 14. The preferred embodiment of the satellite filling apparatus 13o is shown in FIG. lo-12 and 15-19.

Three such identical filling apparatus 13o is preferably fed by the central station loo by means of a pump-supplied supply pipe lol and a pump-supplied or gravity-dependent return pipe lo2.

The central station comprises a circular slurry tank lo3 disposed on a base plate lo4 over a load carrier lo5 and a pair of transverse bending elements lo6. The transducer and bending elements are arranged in the corners of an equilateral triangle. A vertical bucket lo7 is rotatable about a vertical axis in a horizontal plane at the bottom of the tank lo3 and driven by a motor lo8 so as to keep the solids in suspension in the tank lo3. The tank has a lid lo9 with a shielded aperture llo (not shown) through which a powder delivery mechanism 111 can tip powder into the tank lo3.

The powder supply mechanism 111 consists of an elevator 112 with a cradle 113 adapted to engage with a drum 114 of active material and lift it up and around a circular path and tip it into the tank at position 115, shown dotted in FIG. 14. The mechanism 111 is enclosed in a screen 116 as indicated in dotted line in FIG. 14. The tank 13 is filled with water by means of a float cock 117.

Reference will now be made to the preferred embodiment of the p & l filling apparatus shown in FIG. lo-12th This is very similar to the general arrangement of the apparatus shown in FIG. 1-5, and the same reference numerals shall be used for the same parts.

The slurry tank is thus equipped with a bucket 11 located at the bottom of the tank and driven by a variable speed motor 13 over a gearbox 131. A vertical feeder tube 15 with a filter 14o at its lower end extends upwards from a location immediately above the bucket 11 for the input of a MONOPUMP supply pump 16 driven by a variable speed motor 18.

The outlet 132 from the pump 16 is connected to a common supply pipe 133 which extends past a pair of inlet valves 134 and 135 to a pair of filling manifolds 136 and 137 and further to a recirculation tube 138 extending into the slurry tank 1o.

The valve 134 is controlled by a compressed air cylinder 141 and a crank 142 and is arranged to always be open either to the manifold or to bypass. The valve 135 is similarly arranged. The valve 135 is controlled by a similar cylinder 143 and crank 144.

The valves 134 and 135 supply the branch pipes 136 and 137 over pipes 146 and 147 which extend upwards from the valves to the branch pipes, so that any precipitation in these pipes will tend to lie in the region of the valves 134 and 135 and can easily be blotted out. Pressure gauges 148 and 149 are disposed in tubes 146 and 147 and are provided with pressure shut-off means so that as soon as the pressure in tube 146 or 147 reaches a predetermined value which can be preset as desired, cylinder 141 or 143 is automatically activated and the supply from the pump is switched to bypass and returned over pipes 133 and 138 to the tank 1o.

Cylinders 141 and 143 are also arranged to be controlled by switches actuated by a door 15o (although this can be bypassed if desired). When the door is closed over a manifold, e.g. 151 in FIG. 12, it switches the valve 134 from lead to feed and the sludge is delivered to the manifold 136. As the pressure rises and breaks, the door can be swung to the other side to activate the valve 143 for the second filler manifold 137.

The filling manifolds 136 and 137 are associated with bottom terminals 152, only one of which is shown in FIG. laughed at the clarity of the drawing. The branch tubes and bottom clamps are mounted on a backing plate 155 (see Fig. 11), which is inclined rearwardly at a small angle to the vertical so as to facilitate insertion of plates into the clamps and prevent the plates from falling out before the clamps are closed.

The filling manifolds are shown in more detail in FIG. 18 and 19.

Referring first to FIG. 15-17, showing the manifolds consisting of a manifold body 16o bolted to the mounting plate 155 and forming a rectangular horizontal mud distribution cavity 161 which is fed from the rear by means of a central opening 162 to which the tube 146 or 147 is connected. In the middle of the upper side of the cavity 161 is an opening 163 in which the pressure gauge 148 or 149 is arranged.

A series of nozzles 167 extend downwardly from the underside of the cavity 161 out of the body 16o, and it is over these short nozzles that the fabric tube is positioned and secured to it. The clamping is achieved by means of a movable front clamping surface 17o disposed in a frame 23o secured by vertical bolts 171 to the body 16o. The inside of the clamp 17o is a series of rounded teeth as in FIG. 5, · Γ.

17 U1977 but the teeth are jagged as shown in FIG. 17 by reference numeral 172.

The front clamp 17o cooperates with a movable rear clamp 175, and the two clamps are actuated by a pair of pneumatic cylinders 176 mounted on pistons 177 attached to the front clamp 17o.

The cylinders 176 are attached to the rear terminal 175, and when actuated to push out the pistons 177, they thus drive the clan surface 175 rearwardly onto the mounting plate 155 while simultaneously pushing the front terminal 17o forward. The size of this travel can be varied by the adjustable stops 178. The clamp 175 has a round toothed upper edge 18o which clamps the trailing edge of the fabric against the mouthpieces 167, and this edge 18o is also slightly teared, as shown in FIG. 17. The clamp 175 also has a grooved 181 skirt to assist in positioning the plate in the clamp. The plate can thus be placed on the skirt 181 in the correct grooves and then pushed up into the clamp.

As shown in FIG. 18 and 19, the bottom clamp 152 consists of a rear frame 19o bolted to the mounting plate 155 but separated therefrom by a spacer 191 so that liquids exiting from a plate in the clamp can flow down behind it. A pair of side flanges 192 are bolted to the rear frame 19o, and a front frame 193 is hingedly secured by pins 194 to these flanges. At least one of the flanges also carries a stop 195 to prevent the front frame 193 from moving more than 90 ° from the closed position. The front frame is held in that closed position or in the open position of a spring arrangement, with a spring 197 on each side of the clamp extending from a pin 198 on the front frame to a pin 199 on the rear frame.

A finger grip 2oo is attached to the outer upper edge of the front frame. The opposing inner upper edges of the rear frame 19o and the front frame 193 carry cooperatively rounded toothed terminals 2o2 and 2o3, the upper inner edges of which are both raised as shown at 20o4 and 20o5. The clamps are dimensioned so that they press the fabric of the tubes tightly against the extended shoulders 2o7 on the current collecting pins.

A horizontal rod or horizontal projection 208 extends below the clip 203 and is adapted to support the upper rod of a plate and has an opening down through which the patch on the plate can extend.

Each satellite filling apparatus is provided with a work table 22o and drainage duct in the vicinity of the tank 1o. A portion of the work table 22o is shown to the right of the tank 10 in FIG. lo. This provides an area where the plant operator can insert a base rod at the open end of each plate, e.g. a conventional plastic, such as polyethylene plug, which is hammered on the ends of the pins. A weight may also be provided to enable the operator to control the weight of each filled plate.

A monopump (not shown) is placed under the work table in the supply line lol from the tank lo3 to the tank lo and is arranged to pump approx. 45 liters of sludge per per minute into the tank lo which has a capacity of approx. 135 liters. The return pipe lo2 causes a return under the influence of gravity, and the filling apparatus 13o is thus preferably raised on a scaffold approx. 3o cm above floor level. However, a pumped return can also be used if desired.

If desired, a larger tank can be used, e.g. of 225 liters. The sludge in the tank 1o is thus preferably replaced approx. every 5-15, e.g. laughed for minutes.

The device is used as follows:

The sludge is prepared with the desired composition in the tank lO and then continuously pumped through the pipe lol by means of the pump into the satellite tanks lO and recycled therefrom by an overflow pipe arrangement 231 connected to the return pipe lO2.

The weight of the sludge in the tank lo3 is continuously or periodically measured by means of the load transducer lo5, and when it has dropped to a preset value, a warning signal is given to the operator.

The sludge in the tanks 1o is continuously mixed and pumped by the pump 16 through the circuit, the pipe 15, the pump 16, the pipe 132, the valve 134 in the bypass position, the valve 135 in the bypass position and the pipe 138.

A plate comprising fabric tubes assembled on the conductive pins of dimensions appropriate to the top and bottom clamps used is placed in a filling manifold, e.g. 136, and the top and bottom clamps are closed. The door 15o is now closed and if the automatic arrangement is in operation, the cylinder 141 switches the valve 134 to connect the pump 16 to the manifold 136. The plate is filled, the pressure in the manifold cavity 161 is built up and at the preset value the pressure gauge 148 is released which in turn activates the cylinder 141, moving valve 134 back to the bypass position.

As soon as the door 15o was closed, the operator could place a second plate in the manifold 137. Once the first plate has been filled, he can thus start filling the next plate either before or after removing the first plate. The circuit can then be continued until the main tank lo3 requires refilling and this can be done by another plant operator if necessary.

At the end of a shift or when the filling station is to be abandoned, it is convenient that the sludge is pumped from the tank lo back to the tank lo 3 and that the filling station is thoroughly cleaned and its piping system is caused by water.

19 141977

The invention has been explained in its preferred embodiment with reference to the plates being filled while in a substantially vertical plane, and although the plates in FIG. 1-5 being filled vertically, they can be shown in FIG. lo-19 and as shown in FIG. 11 are also filled when placed at an angle of approx. 5 ° with vertical.

Therefore, it will be understood that as long as the layer of active material can be built evenly from the end facing away from the access end with the space between the pin and the sheath filled substantially uniformly on both sides so as not to impair the electrical performance, the exact angle is during which the plate is placed while filtration filling is not critical.

Thus, while it is obviously wise to keep the plate at a steeply inclined angle, there is considerable room for variation. The angle will obviously vary depending on the length and diameter of the plate and the size of the pins. Thus, a very narrow annular space is filled, and as long as the maximum horizontal distance from side to side across the inclined tube is not many times, e.g. no more than 1x times the minimum dimension of the tube or sheath, one can expect that no significant detrimental effect on the uniformity of the filling should occur.

Thus, in general, it may be possible to fill the tubes when they are inclined at angles of up to 6o ° with vertical, although angles up to only 2o ° with vertical are probably more advantageous.

The invention extends in its wider scope of apparatus to a number of additional features.

Thus, in an alternate form, there are at least two filling stations for each pump and sludge storage tank, and the manifolds are fed by a common feeder tube connected from the pump outlet to the recirculation tube and valves are provided to selectively connect each manifold to the feeder tube.

In another modification, the top clamp comprises a fixed toothed side and a movable thus cooperating toothed side adapted to move away from the fixed side while remaining parallel thereto by means of pneumatic or hydraulic means. In addition, to assist the fluid flow from tubes, at least one and preferably both of the opposite sides of the lower edge of the top clamp or the upper edge of the bottom clamp or preferably both clamps are tipped.

Preferably, the back of the top clamp carries a grooved member which extends downwardly therefrom to assist in the placement of a plate in the clamp.

In one embodiment of the invention, the bottom clamp has a front clamping side which is pivotally downward from a rear clamping side, and tensioning means are adapted to press the front plate either towards the closed position or towards a fully open position.

The invention also includes systems for filling accumulator sheath plates comprising a central sludge preparation station and at least one filling apparatus according to prior features of the invention and means for conveying sludge from the central station to the filling apparatus.

The slurry supply means preferably comprise means for continuously feeding sludge to the filling apparatus or each filling apparatus and return means for returning the slurry to the central station whereby the slurry may be continuously circulated.

The slurry preparation station preferably comprises a tank, weighing means which allow the tank to be weighed, stirring means for holding the slurry in suspension, and feedstock for active material and liquid feed means.

The weighing means preferably include a transducer located under the tank.

Preferably, the stirring means comprises a vane adapted to rotate at the bottom of the tank. The invention also encompasses a method of using the plant, which comprises continuously supplying sludge from the central cooking tank to each filling apparatus and back to the central tank at such a rate that the contents of the sludge tank in the filling apparatus are changed at least every hour, and preferably at least every half hour and especially every 5-15 minutes.

In another alternative embodiment (not shown), the three filling apparatus disposed around the central sludge preparation station are! instead of being placed in a straight line with the central station either at the end of the line or in the line between adjacent filling apparatus. Up to six fillers can be fitted with sludge from one central station. In this case, the supply pipe lol and the return pipe lo2 are both provided with a pump, e.g. a MONOPUMP, and may be made of hose or tube with an inner diameter of 2.5 cm.

The viscosity values given herein are used to characterize the slurries as being easily flowable and of low viscosity. The values given in the following Tables 4.7, Io and 15 are the values observed and are not the torque values (as defined herein) used to characterize the preferred sludge. It will be understood that in order to translate the observed torque values in Tables 4.7, Io and 15 to the torque values (as defined herein), the background value of o, o55 must be subtracted from the observed values. Certain examples, e.g. 2 and 24 in Tables 4 and 17,26,34,54,55 and 56 in Table 15 have the same values as the background value, so that their observed torque value is not greater than the background value in the measurement performed and they satisfy the preferred viscosity characteristic by having a torque value (as defined herein) of less than 0.1 o83 kgcra at 20 ° C. Example 1.

An example of a particular plate making method must now be given. This example is carried out on the apparatus described with reference to Figs. 1-5.

The plates were positive plates with 15 tubes, each with a length of 23 cm. The tubes were made of nonwoven polyethylene terephthalate fibers. This is done as follows:

A thin web (1.5 m wide) of fibers with a mean length of 11.4 cm is produced by carding and a web is produced by laying approx. ten webs to form a continuous length of non-woven fabric (ie 1.5 m wide).

The fibers extend substantially longitudinally in the web, which is folded in zig-zag form when taken out from a conveyor moving longitudinally of the web onto a conveyor moving perpendicularly thereon. The fibers thus extend substantially across the length of the web, but due to the migration of the second conveyor, the fibers in adjacent layers are inclined opposite each other at a small angle with the transverse direction.

This material is then impregnated with 50% by weight of polyacrylic binder. It has a thickness of o, 5 to o, 7 mm and weighs 12o to 16o gr./m2.

This material is then transformed into a system of tubes by passing two layers of it through a multiple sewing machine to attach the layers to one another along parallel lines (for example, spaced 13 mm apart) to form pockets or tubes in the usual manner. manner.

This material is then dipped into a phenolic resin and dried. The material absorbs 30% phenolic resin based on the dry weight of the nonwoven material. After cutting the material in length, mandrels of circular cross-section and a diameter of 7.29 mm are then inserted between the rows of stitches to form the pockets. It has an air permeability of 2 8, 0 liters / minute / cm and a water permeability of 1.5 liters / minute / cm area. Its structure is shown in FIG. 9th

As shown in FIG. 9, this nonwoven fabric is formed from randomly entangled single fibers. The fibers have a diameter of approx.

25 microns and more generally 2o-5o microns. The gaps between the individual fibers are generally less than 25 microns and mostly smaller than 10 microns, and furthermore, the material having a thickness of 0.5 to 7 mm has a three-dimensional structure which allows overlap of many individual fibers. in a path from side to side of the plate. The material has an excellent filtration effect for use in accordance with the present invention, as while permitting passage of both liquid and solid in tubular form, it is rapidly filled with active material as it is fed or poured into the tubes under influence. of gravity.

Air permeability was measured as follows: 2

A 2.8 cm diameter (6.16 cm effective cross-sectional area) sample was clamped in place and the time taken for 5o of dry nitrogen to flow through the sample at 20oC under a 1.5cm pressure difference water column, was recorded.

The material is too permeable to mercury porosimetry or air flow through an alcohol-saturated sample to be accurate measurement methods.

However, air permeability is, as is well known, an accurate reflection of the filtering capacity of a material, and materials suitable for use in carrying out the invention can thus be selected by measuring their air permeability.

Water permeability was measured on the same sample by measuring the time it took for a water column originally 42 cm high and 1 liter in volume to flow through the sample under the influence of gravity.

The lower end of the column during the sample was blocked, and water was introduced over the sample, and then the lower end of the sample was opened to the atmosphere.

The sludge used in the following Example 1 was formed from a mixture of 1 part gray lead oxide by weight (mean particle size 20 microns) and 2 parts red lead oxide by weight (mean particle size 5-lo microns) mixed with water tap water at a weight ratio of 1.5: first

The tank lo contained 15o kg of sludge, the bucket 11, which was 76 cm by 3.8 cm, was rotated at 3o-7o rpm. minute to keep the solids in suspension. The pump 16 was operated at a volume passage of 9.5 or more generally 4-l / liter and during recycling the pressure indicator 22 showed zero pressure. Using the same stirring and pumping conditions, valve 23 was switched to the fill position 2. Indicator 22 showed zero pressure for 5 seconds and 1.5 kg / cm after a second when the valve 23 was again switched to 3 recycling. The inner volume of the tubes was lo5 cm.

The volume of sludge passing through the plate was 0, 8 liters, ie. the sludge to inner plate volume ratio was 7.6: 1.

Flow rates below 4 liters per per minute was found to provide rather slow filling speeds, which reduced the productivity of the method and flow rates above 13 liters per minute. per minute, these particular cells showed 23 to provide rather low fill weights for the plates.

Thus, while the sludge is introduced into the upper ends of the tubes, they are filled from the bottom upwards, an oxide layer being built up evenly in the tube, and water and some oxide penetrating through the fabric of the tube, substantially at the level of the upper surface of the active material. the tube.

However, fluid also penetrates throughout the full length of the tube, and it is assumed that additional fluid is squeezed out over the entire length of the tube as the back pressure begins to build up.

The plate was then dried. The plates were weighed and the weight was 45o2o. The plates were then cleaned in the usual manner. Numerous plates were made in this way. Some were analyzed and weighed, and there was no significant weight variation between the upper part, the middle part and the lower part of the tubes. At other plates, the electrical properties were measured and compared to plates with shaken dry powder using the same active material. These plates should be referred to as standard plates.

The plates of the present invention have essentially the same discharge duration at the first and also at the tenth discharge in a standard charge / discharge process, just like the standard plates.

Plates with individual inner tube volumes in the region of 5o-25o cm can be easily filled.

As mentioned above, it has been found that the degree of compression and thus the total dry filling weight of the tubes can be controlled by regulating the pressure which is allowed to build up at the end of the filling period.

Thus, using the same sludge and tubes as described above, it has been found that if the pressure is allowed to build up only 2 + to o, 35 or o, 49 kg / cm, the weight is 42o gr / 5%. If the pressure is allowed 2 + to build up to 1.5 kg / cm, the weight is 45o gr 5%, and if the pressure 2 + is allowed to build up to 2.46 kg / cm, the weight is 5o gr._5%.

Furthermore, the tubes are still uniformly filled without layering using these filling weights.

The active material in the pipes at 45o g filling weight has a density of 4.3 g / cm.

When this example was repeated using a paste of 3 parts of oxide to 1 part of water (which had a density of 3.5 grams / cm), the material was essentially extruded into the tubes which were filled in less than 1 second. No significant amount of liquid passed through the tubes, and upon testing the plates exhibited significant stratification of the tightness of the tubes.

24 141977. Example 2-27.

These examples were carried out on the apparatus described with reference to FIG. 1-5 using the method described for example 1.

The tubes were constructed in the same manner as described for the non-eyed tubes of Example 1, except that they were 36.8 cm long instead of 22.9 cm long.

The nonwoven fabric tubes of Example 1 were used for some of the Examples, as indicated by the letters N-W in Tables 1A and 1B and 2A and 2B below. Two other substances were also used.

One was a spun woven fabric designated S.W. in Tables 1A and 1B and 2A and 2B below, and having an air permeability (as defined herein) of 6.0 liters / cm / minute. It has 17 shooting wires per cm and. 22 threads per cm. The threads are approx. 25o microns in diameter and the filaments approx.

375 microns in diameter. Microscopic examination shows that the spaces between adjacent warp threads and adjacent bullet threads are approx. 25o microns times 25o microns as the maximum, but these spaces are crossed by numerous loose fibers protruding from the threads. Thus, the effective filtration ability of the substance is greatly increased.

The second fabric was a woven fabric referred to as W in Tables 1A and 1B and 2A and 2B below and having an air permeability (as defined herein) of 15.2 liters / cm / minute.

It has 18 shooting wires per cm and 22 warp threads. cm. The warp and weft threads are approx. 25o microns in diameter. Microscopic examination shows that the spaces between adjacent warp threads and adjacent bullet threads are approx. 25o microns by 25o microns and not closed by fibers extending from the threads. Thus, the filtration end of this fabric is much smaller than that of the spun woven fabric.

The compositions used are listed in Tables 1A and 1B and 2A and 2B below.

The sludge was made from mixtures of gray lead oxide (mean particle size 20 microns) and red lead oxide (mean particle size 5-microns) mixed in different weight ratios with tap water.

The solid particles in the sludge were of such a nature that less than 1% by weight was above 2 microns and less than 1% were below ο, οοί microns, while 95% by weight was less than 5 microns. These particle sizes were determined by sieving.

The tank lo contains 15o kg of sludge, the bucket 11 with a size of 76 cm by 3.8 cm was rotated at 3o-7o rpm. minute to keep the solids in suspension. Pump 16 was operated at various volumes as indicated in Tables 1A and 2A. During recycle 25, the pressure indicator 22 showed zero pressure. Using the same stirring and pump conditions, valve 23 was switched to fill position, and the time during which indicator 22 showed zero pressure was recorded and the total time until the time when valve 23 was again switched to recirculation, and the maximum pressure was recorded. These are listed in Tables 1A and 2A. The total internal free volume 3 of the tubes was 17o cm.

Table 3 below provides stratification results for some of the examples and measurements of the porosity of the active material for some of these examples.

Example 7 relates to the woven tube W. Examples 6,9,12,15,16, 19,22 and 23 relate to the spun woven tube SW, and the other examples relate to the nonwoven tube NW. The tubes in all the examples are filled in the same manner as described for Example 1, ie. the solids are filtered off and the solids level gradually rises through the pipes, with most of the liquids exiting from the pipes at the solids level at that particular moment.

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Notes on Tables ΙΑ, IB, 2A, 2B and 3.

1) Solid / liquid ratio.

A) The weights of removed solids in the samples of the filtrates are disregarded, as the weights of these samples were relatively small and there was no way to easily determine the ratio of solids to liquids in the filtrates.

B) The ratios have been calculated taking into account the amount of liquid removed in the paste in the tubes. These conditions therefore slightly underestimate the content of solids in the sludges.

2) Gray / red ratio. These are assumed to remain constant except when extra gray or red oxide is added.

3) Wet paste in plate. The weight of the fabric tube, lead pins and a base bar was 645 gr. The values indicated are the wet filled plate plus a loose bottom bar minus 645 gr.

4)% precipitation of the sample. This is the height A of the solids in the container divided by the height B of the liquids from the bottom of the container, expressed as a percentage after the sample has been thoroughly shaken for ½ minute and then allowed to settle in a vertical position for 24 hours.

The container is a round-bottomed test tube with an inner diameter of 1.5 cm and at least 9 cm of sludge is placed in the test tube.

5) Half-life of the suspension. This is the time taken for the level of the solids in the sample in the container described under 4) to sink to midway between B and A.

The test is performed by affixing a rubber band with its lower edge at the midway level, ie. (B + A) / 2 cm from the bottom of the test tube, vigorously shaking the tube for at least h minute, or until all the solids are removed from the bottom of the test tube, and then aligning the test tube and measuring the time from this point to the moment where light is visible for the first time under the rubber band.

6) Pump speed. This is just an option. The volume of sludge pumped through the manifold was measured by varying settings when collecting the mud as it emerged from the manifold. Two measurements were performed for each pump setting. The sludge volume was measured.

A graph was then plotted for 0, 20, 30 and 40 pump settings of volume relative to time in seconds (using a stopwatch). A fairly straight line of the deposited values was formed.

7) Time until start of pressure build-up. This is the time from the inlet valve opens and until the pressure gauge really starts to move instead of just vibrating.

8) Theoretical volume pumped Until the start of pressure build-up. This is the time under the eighth column from the left in Tables 1A, 2A, 11A, 12A

32 141977

And 13A multiplied by the volume reading'under the seventh column from the left of the said tables and is purely theoretical.

9) Layering. (Table 3). This is determined by cleaning the plates in sulfuric acid with a density of 1,4 ° for 6 hours followed by drying at 82 ° C for 12 hours.

The top bar and bottom bar were then cut from the plate and the remaining portion cut into four equal horizontal strips designated A B C and D with A at the bottom bar end of the plate. These were then weighed. The horizontal strips were then cut into four sections of three tubes, omitting every four tubes, and sections were designated 1-4 by 1 at the lap side of the plate. The four sections 1 from each of the horizontal strips were then weighed, and the value given below 1 in Table 3 is this value. The other vertical sections 2,3 and 4 were weighed in the same way.

10) Pin porosity. (Table 5). This is determined by the well known method of mercury intrusion porosimetry and performed on the same samples as Table 3. Details of this technique can be found in British Patent Specification No. 1,331,257.

The values measured on the rotary vane viscometer for some of the sludges used in the above examples are given below in Table 4.

The viscometer used is shown in FIG. 6.7 and 8.

The apparatus consists of a rack 11 carrying an electric motor 111 driving a vane unit 12o over a gearbox 112 and a torque converter 119. The speed of the gearbox 112 is sensed by a tachometer generator 113 whose output signal is fed to a digital voltmeter 113A. The voltage signal produced by the torque converter is fed to a curve printer 114. The printer has a variable strip speed and a variable scale.

A sample container 13o is firmly supported on an adjustable table 115 which can be raised and lowered on guides 116 by means of a compressed air cylinder 117.

The sample container 13o has a removable lid 131 disposed over the vane unit 12o. The lid can be attached to the container by means of an external bayonet lock (not shown).

The vane unit 12o is removably attached to the output shaft 118 of the gearbox 112 and consists of a central rod 121 with a lower projection 122 which, during use, rests in a hole 132 at the bottom of the container 13o. The bar 121 has a diameter D5 of 1.3 cm and carries three pairs of vanes 123,124 and 125. The vanes 123 and 125 are perpendicular to the vanes 124. All the blades on the vanes are vertical and thus parallel to the axis of the bar 121. The vanes are arranged on arms 126,127 and 128. The distance D6 from the center of the arm 126 to the projection 122 is 6.5 cm, the distance D7 from the center of the arm 127 to the projection 122 is 3.9 cm, and the distance from the center of the the arm 128 of the projection 122 is 1.6 cm. The width of each bucket D3 is 1.2 cm and its height D2 is 1.2 cm and its thickness is 0.1 cm. The distance D4 from the inner edge of each vane to the surface of the rod 121 is 1.5 cm.

The distance D1 between the outer edges of the blades in a pair of blades is 6.8 cm.

The inside height of the container 13o is 8.2 cm and its inside diameter is 8.8 cm. There are four inner shield plates 135 disposed at the ends of diameters perpendicular to each other. The thickness D10 of each screen plate 135 is 0.1 cm and it extends a distance D9 inward of 0.5 cm. The distance D11 between the cutting plates on a diameter is 7.65 cm. Each screen plate extends to the full height of the container.

The container and shield plates are made of smooth stainless steel.

The device is used as follows:

The container is filled to a depth of 8.2 cm with the material to be examined and raised into place clamped to the table 115 and the lid 131 secured.

The curve printer 114 is started and the motor 111 is then started with the exchange set to a low shear rate, e.g. six turns per minute. The starting torque and the stationary torque are detected by the torque converter 119 and the motor and the printer run until a stationary value has been recorded for at least two minutes. This is the stationary torque value. The stationary torque value is noted and if there was an initial maximum, this ratio is noted. The sample is then removed and shaken with the amount of material being measured and the container refilled. The measurement is then repeated at a higher shear rate, e.g.

18 rpm minute. This cycle is repeated for as many shear rates as desired.

The background torque value, namely, with the container 13o empty, was found to be o, o55 kgcm at all the shear rates given in Table 4. The same value was obtained when the container was filled with water.

The torque value defined herein measured on the rotary vane viscometer is the value of the stationary torque of the sample measured in the manner described above on the apparatus described above at a shear rate of 6 revolutions of the vanes per per minute at an ambient temperature of 20 ° C minus the background value at 20 ° C.

34 141977

Table 4

Example Gray Solid% sulfa- Viscosimeter with rotary wing Red fabrics tering of ~! T- ΓΤ 7 Π7, Γ oxide 555kSr gray oxide Shear Torque Occurrence 3 speed kg kg cm of max. mum

Together- 75:25 2.90: 1 12.6% 6 50.0 Yes Equation Example 1 of German publication script 2,243,377 2 33:67 1.49: 1 none 6 0.069 No 42 0.055 No 17 66:34 2.00: 1 none 6 0.111 No 24 66: 34 0.54: 1 none 6 0.055 No 26 100: 1 1.65: 1 none 6 0.083 No 24 0.069 No 42 0.069 No

footnote:

For viscosity values, see general note before the examples.

35 141977

Table 5

Example 18 2o 24

Pores between porosity (%) provided by pores of such dimensions 100 - 50 microns 0.9 0.7 0.6 50 - 25 "0.8 0.4 0.4 25 - 12.5" 0.2 0.1 0.2 12.5 - 6.4 "0.2 0.1 0.2 6.4 - 3.2" 0.1 0.1 0.1 3.2 - 1.6 "0.4 0.3 1.6 - 0.8" 0.2 0.1 0.5 0.8 - 0.4 "1.3 1.1 2.3 0.4 - 0.2" 3.3 4.9 4.9 0.2 - 0.1 "5.5 4.6 4.1 0.1 - 0.05" 3.3 3.2 3.6 0.15 - 0.035 H 0.8 0.9 0.9 below 0.035 "2.1 1.0 1.2 total porosity 19.1 17.5 19.0 apparent density 5.5 5.6 5.4 true density 6.8 6.7 6.7 36 141977

It has been found that for oxides to water ratios above 2.5: 1 the filtration process does not take place and the process is much more difficult to control. Thus, there is a tendency for the plates to become overcrowded and too dense, and for the pipes to fill unevenly, with large pockets and gaps prone to arise and also areas of lower density distributed unevenly throughout the plate.

For oxide-water ratios below 0.4 to 1, the time taken to fill the plate becomes too long, and the weight of oxides which can be introduced into the tubes tends to fall to unacceptably low values.

It is preferred that the weight of wet paste in the plates used in Examples 2-27 be at least 800 grams and preferably is in the range of 8oo to 95o grams.

As can be seen from Table 4, the viscosity of the aqueous mud used in accordance with the present invention is all very small and is substantially the same as the viscosity of water compared to the viscosity of conventional battery pastes and the paste of Example 1 of the present invention. German Petition No. 2,243,377. Compared to a torque value measured on a rotary vane viscometer for the German presentation of 5o kgcm, typical flowable self-leveling sludges of the present invention have values below 0, 138 kgcm and especially no greater than o, 111 kgcm.

Examples 28-33

These are examples of high viscosity mixtures and are given for comparison only and are not in accordance with the present invention.

These are examples of the use of designs having a torque value measured on rotary vane viscometer (as defined herein) of o, o83 kgcm and above. Examples 28-33 were performed on the apparatus of FIG. 1-5. Example 33 was performed on the apparatus of FIG. lo-19th This apparatus differs from the previous apparatus only at the delivery rate of the monopump, the use of a preset pressure-sensitive switch which automatically interrupts the sludge supply as soon as the pressure in the manifold supply pipes reaches a preset value and at certain mechanical engineering characteristics.

The relationships between the constituents and conditions used in these examples are given in Tables 6A and 6B below.

The viscosities of the embodiments used are given in Table 7 and the stratification results for example 33 in Table 8.

None of these designs were filled by the filtration filling method, all being filled from the inlet end downwards. Some designs, such as Example 30, were too thick to pump into the tubes. In Example 31, not all the pipes were filled correctly. As shown in Table 8, the density of the active material in the plate varied

JL

Example 33 with significant sizes, namely ^ 20% compared to the maximum variation in Table 3 of ^ 4%.

It has also been found that the use of these higher viscosity pastes tends to cause occasional blockage of the machinery during use.

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Table 7

Example, <^ ra't Solid% sulfa— Visco simeter with rotating vinae Red substances tering of ~ '--- i-3 oxide liquids gray oxide Shear Torque j Occurrence speed kg cm f of max— ___, ___ rpm .__ mum__

Together— 75:25 2.90: 1 12.6 6 50.0 Yes equation!

Example | 1 in German publication script 2,243,377 28 "3.30: 1 none" 0.194 29 66:34 2.57: 1 "" 0.235 30 75:25 2.86: 1 3.75 "0.91 31" 0.70: 1 9 "0.166 32 66:34 0.73: 1 "" 0.138 33 100: 0 0.90: 1 17 "0.138 No.

footnote:

For viscosity values, see general note before the examples.

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It has been mentioned above that other electrochemically active materials, in addition to lead-acid materials, can be used in the process of the invention.

Obviously, the ingredients used in such alternative arrangements must be compatible with each other. Thus, when e.g. to use alkaline negative active materials, the pins must be made of a metal with sufficient chemical corrosion resistance to the alkaline environment, e.g. round or strip-shaped steel flow collection pins may be used and these may be nickel plated and the polyester fabric tubes may be replaced by polyamide, e.g. nylonstofrør. Preferred examples of alkaline electrochemically active materials include nickel hydroxide for the positive plate and cadmium hydroxide for the negative-ve plate. These typically contain a proportion of electrically conductive material, e.g. graphite which is sufficient to ensure adequate conductivity, preferably 5-15% by weight of graphite is used. Steel can be used as the stream collecting element and can also be used as the casing for the active material in a suitable porous form to enable filtration filling to be achieved. Other alkaline electrochemically active materials include iron oxide to the negative active material.

Nickel hydroxide may also have nickel particles or flakes distributed therein to increase its conductivity. The iron oxide may also have conductive materials added to improve its conductivity.

The electrolyte is typically aqueous potassium hydroxide, which may contain a small proportion of lithium hydroxide.

Various types of electrochemically active lead-acid material have already been mentioned, including gray lead oxide and red lead oxide. Gray lead oxide comes in various forms with different content of lead and lead monoxide (PbO) and particle sizes depending on the process by which it is produced. Hardinge oxide produced by ball milling of lead bars has a lead content of approx. 2o-4o%, e.g. 3o%, and a PbO content of approx. 8o-6o%, e.g. 7o%.

It is subjected to air classification by returning the coarser particles for repainting. It has an average particle size of 15-25 preferably 20 microns.

Tudor oxide is another oxide produced by paint, but this is not subject to air classification and has a mean particle size of 3o ~ 5q, preferably 4o microns.

Oxide produced by the roasting process (e.g. the Barton pan process) has an average particle size of 12-15 microns.

As the invention enables the use of chemically inactive sheaths, it does not preclude filling the tubes with metallic forms of the active materials, and their chemical or electrolytic conversion into electrochemically active form in the sheath, and the invention thus encompasses such a broadest aspect. arrangement. Thus, the term active material composition includes materials which are capable of being converted into electrochemically active form in the porous sheath either before mounting in the cell or after mounting in the cell.

There are many other electrochemically active pairs that have been proposed for use in accumulators.

The method has so far been described with reference to secondary or rechargeable systems. However, it is equally applicable to primary battery systems where the active materials or one of them can be enclosed in a porous sheath and introduced into the sheath to scan a liquid, preferably water, slurry.

The liquid used as the suspending agent in the sludge is simplest aqueous, and this is obviously preferred for reasons of price, safety and inactivity. However, if an aqueous agent should cause problems, it can be replaced by any other liquid agent suitable for the active material used.

Examples of other battery systems by which the method may be used are thus given in the following Table 9.

The active materials listed below are to be used in particle form with a particle size suitable for providing filtration filling with the porous sheath to be used.

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Tests have shown that nonwoven tubular sheets can be filled by the filtration filling process using either positive alkaline active material or negative alkaline active material.

Thus, it has been found that usually negative alkaline active material (containing by weight 76% cadmium hydroxide, 5% cadmium metal, 15% iron oxide, 2% graphite and 2% paraffin) can be introduced alone under the influence of gravity in the same woven tubular sheets NW used in Examples 2-27. It has been found that the ratio of active material to water in the range o, 75: 1 down to o, 2: 1 produces sludge which satisfies from the bottom end of the pipes back towards the entrance with a good even distribution of active material in the pipes. The solids in these sludge settle relatively quickly in the same manner as the lead acid sludge described above and are all easily flowable liquids.

Similarly, usual positive alkaline active material compositions (containing by weight 85% nickel hydroxide and 15% graphite (a mixture of powdered graphite and flake graphite)) when used in the same solids-liquid ratios, produce sludge that is filled from the bottom ends of the tubes back towards the entrance with a good even distribution of the active material in the tubes.

The solids in these sludges settle again relatively quickly in a similar manner to the lead acid sludge described above and are all easily flowable liquids.

Experiments using pressure on the sludge showed that the amount of active material introduced into the tubes can be increased by the application of pressure in a similar manner as shown above in connection with active lead acid materials.

Another factor to be remembered for achieving successful filtration filling is the relationship between sludge particle size and permeability, structure and pore dimensions, ie. the filtering ability of the material from which the porous sheath is made. With a very porous sheath, such as the woven sheath described in connection with Examples 2-27 and especially Example 7, the mixture of gray Hardinge oxide and red lead oxide was 33:67, which has a relatively small particle size at a solids ratio. and liquids of only 1.35: 1, as in Example 7, thus unable to fill the woven plate, since the layer of active material was unable to build up within the tubes.

However, when loo% gray Tudor oxide of medium particle size 4 microns is used at solids to liquids ratio of 2.5: 1 to 2.0: 1, these woven tubes, W, can be filtered satisfactorily. These tubes can also be filled satisfactorily by using this range of solids-liquid ratios in the sludges, wherein the ratios of Tudor oxide to red lead oxide are 8o: 2o, 6o: 4o, 4o: 6o and 2o: 8o.

These tubes can also be filled with Hardinge oxide and mixtures of Hardinge oxide and red lead oxide in the ratio of 8o: 2o at these ratios of solids and liquids.

The invention has hitherto been described with reference to active lead acid exx materials which have not been acidified. However, active lead acid materials may also be used to which acid has been added to at least partially sulfate them.

It has been found that the addition of acid has a pronounced effect on the viscosity of the sludge within certain sulfation grades.

The reason for this effect is not known for certain, and although the invention does not depend on any particular theory, it is believed that this may be due to variations in the degree of hydration and thus interactions "in" the interior of molecules or particles with variation in the amount of medium. Figures for torque values measured on rotary vane viscometer and given below in Table I1 clearly show this variation in viscosity with variation of degree of sulfation.

Thus, care must be taken to use a system where the ratio of solids to liquids is kept sufficiently low so that the percent sulphation used does not cause the sludge, when used with the particular dust jacket, to be unable to filtering fill it.

It has also been found, at least using the non-woven fabric NW described above with a wide range of lead-acid mud, that sludge having a torque value (as defined herein) measured on a rotary vane viscometer, at less than o, o83 kgcm at 20 ° C seems to be filled by filtration filling, while sludge with such torque values of o, o83 kgcm and above is filled by injection filling. Thus, although the invention in its broadest aspects is not limited to the use of sludge with torque values below 0, o83 kgcm, the use of such sludge is much preferred.

In the following Examples 34-42, certain illustrative non-limiting examples of slurry with added acid are provided which are filtered.

1 gram of gray lead oxide requires 0.4 ml of sulfuric acid of density 1.4 to obtain 10% sulfation.

With gray lead oxide containing 3o% lead and 7o% lead oxide, the degree of sulfation, ie. % lead sulfate given by the equation: 48 141977 volume of H 2 SO. of Density 1.4 in Ilter Y = 216.4 - i— -: -—- Weight of gray lead oxide in kilograms

Examples 34-42

These were performed on the apparatus described with reference to FIG. 1-5. '

The conditions and conditions and results used are listed below in Tables 11A and 11B. In all these examples, loo% Hardinge oxide with solids to liquids ratio of 1.28: 1 down to 0.43: 1 and nonwoven tubes is used.

It will be noted that with these slurries with added acid, slightly lower values are obtained for the wet paste in the plate compared to the slurries without added acid in Examples 1-27. As can be seen in Table 14 below, the active material in the tubes has a lower density and has good distribution and no harmful layering.

The viscosities of the slurries used in Examples 34-38 are given in Table 15.

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Examples 43-5o

These were performed on the apparatus described with reference to FIG. 1-5.

The conditions / conditions and results used for these examples are given below in Tables 12A and 12B. In these examples, large proportions of red lead are used with solids-liquid ratios of approx. 1.6: 1 and nonwoven tubes, NW.

Layering results are given in Table 14.

The viscosities of mud used in Examples 44,47,48 and 5o are given in Table 15.

The degree of sulfation given in Table 12A is obtained by simply replacing the weight of gray lead with the weight of red lead. The sludges of Examples 47-5q were prepared by adding gray lead oxide to the sludge of Example 46.

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Examples 51-56

These were performed on the apparatus described with reference to FIG. lo-19th

The conditions / conditions and results used for these examples are given in Tables 13A and 13B below. In these examples, large proportions of gray lead oxide and higher sulfation rates are used than in Examples 34-42 with nonwoven tubes.

Layer results are given in Table 14 and the viscosities of the sludges used in Examples 51.54.55 and 56 are given in Table 15.

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ni +> * B O Η H O O O O O O

fe a> ________ sp ho ·· · OOO ·· m ·· m -P -P .. o vs h ·· ·· ·· oo m · m · «(dti OH. co OOO ·· · m ·« * Η Όν o · oo OOO cm "Μ * H m ^ p 0 fe HOHH η Η σ <com § niroOH om ro> * mvo μη« p * pmmm m.in mm A! (!) Fe ft ___! _ L ___ J ___- 1__ : --- 59 14Ϊ977

Jabel 15

Example Gray Solid% sulfa- Viscosimeter with rotating wine Red substances tering ~ 'I-! in 3 oxide liquids Shear Torque I Occurrence.

speed kg cm of iaaksi- rpm / rain. mum 34 100: 1 1.28: 1 1.5 6 0.111 No 29 0.111 No 42 0.097 No 38 100: 1 0.47: 1 1.5 6 · 0.069 No 24 0.069 No 42 0.083 No 41 100: 1 0.43: 1 4.0 6 0.055 No 24 0.055 No 42 0.055 No +2 44 0: 100 1.59: 1 0.18 6 0.055 No 24 0.069 No 42 0.069 No 47 9.9: 1.62: 1 0.72 6 0.055 No 90 1 24 0.069 No 42 0.069 No 48 18.6: 1.68: 1 0.72 6 0.055 No 81: 9 24 0.055 No 42 0.055 No 51 100: 0 0.49: 1 16.7 6 0.069 No 24 0.069 No 42 0.069 No 54 92: 8 0.50: 1 16.6 6 0.083 No 24 0.055 No 42 0.055 No 55 84.5: 15. 0.52: 1 16.1 6 0.097 No; 5 24 0.069 No 42 0.069 No 56 55.5: 44. 0.78: 1 10.6 6 0.083 No 5 24 0.069 No 42 0.069 No

footnote:

For viscosity values, see general note before the examples.

6ο 141977

Comparison of the stratification results in Table 8 and Table 14 shows that filtration-filled plates (Table 14) have significantly lower stratification rates than injection-filled plates (Table 8).

Notes to Tables 11A and 11B to 13A and 13B.

1)% sulfation. It has been assumed that all the acid is absorbed by and reacts with the excess oxide at the stage of first addition and thus the% sulfation remains constant until more acid is added, ie. part of the acid is removed with each paste sample removed.

2) Ratio of solids to liquids.

These are intended to include any acid added as a liquid.

The effect of pre-sulphating the active lead acid material has been described with reference to three areas of the possible theoretical range of sludge compositions. These are loo% gray oxide with solids to liquids ratio of 1.3: 1 to 0.4: 1 and sulphation rates in the range 1.5 to 4, o% (Examples 34-42)} o: loo gray to red to 2o: 8o gray to red with ratio of solids to liquids in the range 1.5: 1 to 1.7: 1 and sulfation rates in the range o, o5 to o, 8% (Examples 43 to 5q)} and loo: o gray to red to 55:45 gray to red with ratios of solids to liquids in the range o, 4: 1 to o, 8: 1 and sulfation rates from lO% to 17% (examples 51 to 56),

It is believed that there are many other embodiments of pre-sulphated active lead acid materials which will be effective in providing filtration filling, and with the teachings herein set forth on the effect of acid on the viscosity and the effect of the variation of solids-liquid ratio and of the effect of acid on the viscosity and the effect of the variation of the ratio of gray oxide to red oxide and the effect of the variation in the permeability of the porous sheath will readily enable the reader to select a suitable embodiment and material for the porous sheath.

Claims (34)

6i 141977 Patent Claims. A method of producing sheath plates for accumulators and batteries by introducing an active material composition containing liquids into the porous sheath of the plate when the sheath is placed on the conductive element of the plate, characterized in that the active material in the composition is introduced into the sheath as an aqueous slurry comprising an active lead-acid composition or a convertible material having a torque value measured on rotary vane viscosimeters of less than 0.0081 Nm at 20 ° C, which aqueous mud is introduced into the jacket at a pressure less than 34.3 kPa until the casing is filled with the composition, with liquid exiting through the walls of the casing and the pressure thereon allowing to rise to a value above 34.3 kPa, but not above 686 kPa, after which the pressure is relieved. Process according to claim 1, characterized in that the sheath is arranged in a substantially vertical plane and that the aqueous sludge has a ratio of active material to water in the range 0.4: 1 to 2.5: 1 in proportions according to weight, the material of the sheath being selected to filter out active material while allowing the passage of liquids, the solids being at least partially retained in the sheath and the liquids at least partially passing out through the sheath walls. Method according to claim 2, characterized in that the ratio between the volume of sludge introduced into the sheaths and the total internal free volume of the sheaths in the plate is at least 2: 1. Method according to claim 3, characterized in that the ratio between the volume of sludge introduced into the sheaths and the total internal free volume of the sheaths in the plate is between 3: 1 and 15: 1. Process according to claim 1,2,3 or 4, characterized in that the aqueous mud comprises an aqueous mixture of particulate active material and liquids, the weight ratio of the solids to the liquids being in the range of 1: 1 to 1.8: first Process according to any one of claims 1-5, characterized in that the sludge has a density of less than 3 gr / cm. Process according to any one of claims 1-6, characterized in that after the casing has been filled, the back pressure in the mud supply to the casing is allowed to build up to a pressure in the range 34.3 to 343 kPa. Process according to any one of claims 1-7, characterized in that the material of the jacket has a nitrogen permeability in the range of 0.5 to 20 liters / cm 2 / min. 62 141977 Process according to claim 8, characterized in that the material of the jacket has a nitrogen permeability in the range of 2 3-l / liter / cm / min. Method according to claim 9, characterized in that the material of the jacket is a nonwoven polyester fiber sheet which is 2 o, 5 to o, 7 mm thick and weighs 12 o to 16 o grams per hour. m and has a nitrogen permeability of 8.0 liters / cm / min. and a water permeability of 1.5 liters / cm / min. Process according to claim 1, characterized in that the sludge composition is non-acidified and contains gray lead oxide and red lead oxide in a range by weight ratio of 66:34 to 33:67 and with the weight ratio of solids to liquids located in the region 2 , o: 1 to 0.5: 1. Process according to claim 11, characterized in that the weight ratio of solids to liquids is in the range 1.5: 1 to 0.7: 1. Method according to claim 8, characterized in that the material of the sheath is a spun woven fabric with 15 to 25 weft threads. cm and 15 to 25 warp threads. and a nitrogen permeability of 5 liters / cm / min. Process according to claim 13, characterized in that the sludge composition is non-acidified and contains gray lead oxide and red lead oxide in a range by weight ratio of 66:34 to 33:67 and that the weight ratio of solids to liquids is in the range. 2.5: 1 to o, 9: 1. Process according to any one of claims 1-14, characterized in that, as the active material, an active lead acid material is used which is at least partially sulphated before being introduced into the porous sheath of the plate. Process according to claim 15, characterized in that an active material is used, the degree of sulfation of which is less than 17% by weight. Process according to claim 16, characterized in that an active material is used, the degree of sulfation of which is in the range of 0, 0% to 16,7%. Process according to claim 15, characterized in that gray lead oxide is used as the active material and the degree of sulphation is up to 4% and the ratio of solids to liquids is in the range of 1.3: 1 to 0.4. : l. Process according to claim 15, characterized in that gray lead oxide containing up to 45% by weight of red lead oxide is used as the active material, and that the sulfation gradient is in the range 100% to 17% and the ratio of solid substances and liquids are below 0, 8: 1. Process according to claim 15, characterized in that as the active material red lead oxide containing up to 20% by weight of gray lead oxide is used and that the degree of sulphation is up to 0,8% and the ratio of solids to liquids is not is more than 1.7: 1. Process according to any one of claims 1-14, characterized in that an active material having an average particle size in the range 1 to 10 microns is used. Process according to claim 21, characterized in that an active material having an average particle size in the range 5 to 20 microns is used. Process according to any one of the preceding claims, characterized in that the weight ratio of the active material in a continuously mixed sludge supply to the individual filling weight is in the range 136o: 1 to 25: 1. Apparatus for filling accumulation plates for accumulators or batteries by the method according to claim 1 or 2 and comprising at least one filling station (20), the plate being supported with its sheath mounted on its current conducting element in a substantially vertical plane, and a filling manifold (24) disposed adjacent to the upper portion of the support means (29-31), and a mud storage tank (1o) provided with stirring means (11) for holding the active material in the storage tank in suspension as a mud, characterized by supply means (15-19) are connected between the storage tank (1o) and each filling station (2o) to deliver the sludge from the storage tank to the manifold (24) in a selected filling station (2o), that means (1o) are placed below the filling station for collecting the fluids exiting through the walls of the sheaths that the delivery means include recycling means (23, 26) for recycling the sludge to the storage tank (lo) when the sludge is not delivered to a filling station (20), said filling station having a frame (29) rigidly attached to said filling manifold (24) and carrying top and bottom clamps (3o, 31) adapted to releasably clamp the plate to said frame, and said manifold ( 24) has a discharge nozzle unit consisting of rigid feed tubes (55) spaced apart at a straight line with their centers on the centers of the plate (5o) and with outside diameters corresponding to the inner diameters of the plate tubes. Apparatus according to claim 24, characterized in that the delivery means for the manifold comprise a pump (16) with an inlet pipe (15) which communicates with the storage tank (lo) and valve means (23), the recirculation valve, which is associated with the discharge of the pump to direct sludge from the pump outlet to a filling station (2o) or to recycle the sludge to the storage tank. Apparatus according to claim 24, characterized in that the clamps (30, 31) are toothed and conformed to the outer surface profile of the bottom and top of the tubular plate. Apparatus according to claim 24 or 26, characterized in that at least the top clamp (30) is provided with an elastic sealing liner. Apparatus according to claim 24, characterized in that the feeder tubes (55) extend through an elastic gasket (58) such that the frame (29) has such dimensions relative to the plate that the end of the plate must be pressed into the gasket (58). to place the plate in the supporting members (29-31). Apparatus according to any one of claims 24-28, characterized in that a pressure-sensitive valve is arranged in connection with the inlet side of each filling manifold (24). Apparatus according to any one of claims 24-29, characterized in that there are at least two filling stations for each pump (16) and sludge storage tank (lO) and that the recycling valve is a three-way valve. Apparatus according to any one of claims 24-29, characterized in that there are at least two filling stations for each pump (16) and sludge storage tank (lO) and that the manifolds (136, 137) are fed by a common feeder tube (133 ), which is connected between the outlet (132) of the pump (16) and the recirculation tube (138) and that valve means (134,135) exist to selectively connect each manifold to the feeder tube (133). Apparatus according to any one of claims 29-31, characterized in that the pressure-sensitive valve is a pressure relief valve. Apparatus according to any one of claims 29-31, characterized in that the or each pressure-sensitive valve is adapted to activate automatic switching of the recirculation valve or valve means connecting the manifold (20) or each manifold to the common feeder tube (15). ) to the recycle position and to relieve the pressure in the supply line to the plate as soon as a preset pressure is reached. Apparatus according to any one of claims 24-33, characterized in that the top clamp has a fixed toothed side (17o) and a movable thus cooperating toothed side (175) adapted to move away from the fixed side. while remaining