DE2558011A1 - Accumulator plates prodn by filling porous sheath with slurry - with high liquid content filtered by sheath, for simplicity - Google Patents

Abstract

In the prodn. of armour plates, esp. for accumulators, by introducing an active compsn. contg. liquid into the porous sheath of the plate when the sheath is placed on the current-carrying element of the plate, an alkaline active compsn. is used with a liq. content so high that the active matl. is filtered out by the porous sheath, whilst liq. penetrates its walls. The process is simpler than the usual multistage process and eliminates the problems associated with handling a dry powder.

Description

Method and device for producing accumulator tank bursts The invention relates to a new process for the production of alkaline batteries and a new electrode design for performing the method.

The traditional method of manufacturing alkaline batteries, for example with a positive nickel electrode and a negative cadmium electrode, consists in using a perforated steel sheet with perforations from 0.2 to 0.25 mm diameter deformed into a narrow channel section, a briquette of positive or negative active material obtained by compressing the powdery active Material has been produced, insert it into the channel, then another sheet made of perforated steel above the assembly and all around with the edge of the Flanged arrangement to close it.

The channel strip is then cut to length and side by side arranged with other strips to form the required cell size. After this the arrangement has been welded into a steel sieve container, becoming current collectors appropriate.

This process is a multi-step process, and there is a need to simplify this process. It also prepares handling of the dry powder poses significant problems.

It has now been found that these problems are greatly reduced can if one modified the active material in a new process and introduces new plate shapes.

The plates are armor plates, preferably tubular plates.

In the following, the term "tube plate" is used for the case where the individual conductive elements (cores or discharge pins) each from a jacket pipe, separated or connected, are encased, while the designation "Armor plate" is not limited to the case of the tubular plate; rather can the covering arranged around the souls have any shape.

The casing tubes of the tubular plates can be made of a wide variety of materials exist and be arranged differently. You can, for example, with each other be connected, or it can be separate jacket pipes that are separated are arranged on the conductive elements (conductor pins) of the cell.

An example of such a separate jacket pipe arrangement exists in that one uses fabric jacket pipes with a thin outer plastic sheath, the perforations about 1 to 2 mm in diameter at intervals of about 1 to 2 mm owns.

This plastic casing has a thickness of about 0.1 to 0.2 mm.

Although the invention is not limited to such arrangements, their description takes place in particular with regard to casing pipe arrangements which the casing pipes represent a single, preformed production part, as this the order of the casing pipes on the conductive elements of the Plate relieved.

It has been found that such armor plates or tubular plates The filling process can be done quickly and evenly by keeping the alkaline active Material in the tubes in the form of a pourable, liquid sludge very lower Viscosity under gravity pours or introduces into the jacket pipes and, after the casing pipes are filled, preferably by increasing the pressure or Back pressure compressed.

By controlling the pressure value to which you can increase the counter pressure can, the degree of compression can be changed at will, and it can be very achieve uniform compaction.

The invention thus provides a method for producing Armor plates for alkaline batteries by introducing an active mass in the porous envelope of the plate, which is characterized in that one alkaline active mass with such a water content that active material is used is filtered out through the porous envelope, while liquid is filtered out through the walls able to emerge from the porous envelope.

Preferably, the liquid content of the mass is so large that a Bed * active material is built up in the envelope, with the bed starting out from the end opposite the feed of the mass, back to the end of the Feeding the mass builds up, and liquid through the walls of the envelope during the period of bed construction passes through.

The active material is preferably a positive one nickel active material or a negative cadmium active material. The weight ratio from solids to water in bulk is preferably 3.0 s 1 or more to down to preferably 0.1: 1, with ratios of 2.5: 1 to 0.1 s 1 being preferred and ratios from 1: 1 to 0.25: 1, in particular 0.75: 1 to 0.3: 1 are particularly preferred.

When using negative active cadmium material it has been shown that at ratios above about 0.8: 1, for example 0.96: 1, the sludge are very thick and there is very little settling during 24 hours. For the filtration filling are therefore preferred cadmium hydroxide sludges that are stop very quickly.

The term "casing" includes both arrangements of separate jacket pipes as well as arrangements of casing pipes that are connected to one another or made of flat Material are made. Any wrappings come into question, provided that these a pouch or pouch around the electroconductive element or elements of the plate and active material as a bed around the conductive element or elements to filter around.

In a preferred embodiment, the invention relates to a method for the production of armor plates, preferably tubular plates, for alkaline Accumulators, by introducing an active material into the porous envelope of a encased plate, for example the casing pipes, if the casing pipes on the conductive Element of the plate, for example the souls or

Conductor pins, are arranged, which is characterized by that the alkaline active mass is fed into the casing as aqueous sludge, if the casing is equipped in a substantially vertical plane, preferably with vertically aligned casing pipes so that the solids move to the bottom the envelope can settle under the force of gravity, whereby the aqueous sludge preferably a weight ratio of active material to water in the range of 2.5: 1 to 0.1: 1, the material of the envelope is selected to be filtering out active material while letting liquids pass through, thereby the solids are at least partially held within the envelope and the liquid exits at least partially through the walls of the envelope, and man the feeding of the sludge into the casing continues until the casing is filled with active material, whereupon the pressure in the feed to the envelope to a value of more than 0.35 kg / cm2 (0.35 atü), but not more than 7 kg / cm2 (7 ast), can rise and then brings about a pressure release. Below is that Process of the invention essentially with reference to the manufacture of tubular plates described.

The ratio of the volume of sludge that is fed into the casing pipes is, to the total inner free volume of the jacket pipes in the plate preferably at least 2: 1, in particular at least 3: 1, 4: 1 or 5: 1, with a range from 5: 1 to 15: 1 being preferred and a range from 6: 1 to 10 being preferred : 1 is particularly preferred. The inner free volume of the jacket pipes is it is the volume within the clear diameter of the casing pipes, that is not occupied by the conductive elements.

The aqueous sludge is a mixture of water and particulate active material.

The preferred weight ratio of solids to be used Liquid in the sludge moving within the aforementioned range, depends on the active material used and the permeability or permeability of the jacket pipes to be filled.

The aqueous sludge is preferably a mixture made of nickel hydroxide and particulate active graphite material and water in one Weight ratio in the range from 0.5: 1 to 1.5: 1, or around cadmium hydroxide-cadmium-graphite mixtures and water in a weight ratio ranging from 0.25: 1 to 0.75: 1.

The positive active nickel material can be 80 to 90 percent nickel hydroxide included, the remainder being graphite, preferably in the form of a Mixture of powdered graphite and flaky graphite, preferably in a weight ratio from 20:80 to 80:20, for example 66:34.

The cadmium negative active material preferably contains 70 to 90 Percent cadmium hydroxide with up to 10 percent, for example 3 to 7 percent, cadmium, up to 5 percent, for example 1 to 3 percent, graphite, and up to 5 percent, for Example 1 to 3 percent, iron oxide.

The solid particles in the sludge preferably all have one Size less than 1000, with preferably at least 90 percent less than 500 P and at least 50 percent less than 150 P. In a particularly preferred one Embodiment 100 percent by weight have a size of less than 500 tr, where Are no more than 25 percent below 45 P. All percentages relate to focus on weight; the determination is made by means of sieve analysis.

Possess the sludges or suspensions preferred according to the invention Viscosities that essentially correspond to the viscosity of water. This is a fundamental difference to conventional accumulator pastes. The viscosities of these preferred slurries cannot be measured with a Brookfield viscometer measured as the solids settle on standing.

The sludges preferred according to the invention can be poured easily, and the solids settle out of the liquid phase quickly, that is, in less than 15 minutes when left standing.

The compositions used according to the invention are thus preferably characterized characterized in that they have a rotary vane viscosi meter torque value (description see below) of less than 0.83 g. m (0.006 lbs. ft), preferably not over 0.55 g. m (0.004 1t3. ft), each measured at 20 On own.

The suspension half-life (as described below) of the slurries is preferably no longer than 15 minutes and is in particular in the range of 1 to 10 minutes.

The sludge is preferably introduced into the casing pipes under gravity, that is, at a pressure or overpressure of zero or under 0.35 kg / cm2, until the casing pipes are filled with the mass. Then lets one the pressure resp.

The overpressure does not rise to a value of more than 7 kg / cm2 and then brings about a pressure release.

In one embodiment, the casing pipes are filled in essential by gravity. Then you let a pressure build-up take place, to put pressure on the active material in the filled jacket pipes, for example for exercise a fraction of the time it takes to fill the jacket tube So, for example, a pressure in the range of 0.35 to 3.5 kg / cm2, for example 0.7 to 2.1 kr / cm2, for example for 1/10 to 1/2 the time, or for the same Time required to fill the jacket pipe.

For example, if it takes 5 to 15 seconds to fill the jacket pipe If necessary, the pressure is applied for a period of 1 to 5 seconds, for example.

In a further embodiment, the pressure is applied over a longer period of time Period applied. The filling of the Kentei pipes is essentially done here by gravity by putting the mud into the jacket pipes under a counter pressure pumped in by O When the jackets are full, pumping continues, and the back pressure is allowed to rise to a value not exceeding 4.9 kg / cm2. The pressure can thus be in the range from 0.35 to 3.5 kg / cm2, for example 0.7 to 2.1 kg / cm2, lentils. The weight of the oxide in the jacket pipes can be adjusted by regulating the Pressure build-up can be controlled, as shown in the example len. In general one leaves the pressure only up to increase by a specified value and then brings about a pressure release.

As explained above, the material of the jacket pipe is selected so that that it has a filtering effect on the active material used. this means but not that all of the active material is removed from the liquid, which exits through the casing pipes, but only that a part in the casing pipes is held back.

As stated above, the ratio to be used depends on active material to liquid depends on a variety of factors including the nature of the material from which the casing pipes are made.

According to the invention, a compromise must be made between the requirement to the material to have high water permeability in order to have good conductivity to ensure when using the accumulator, and the requirements for the material, to have a good filter effect, so that the filling process can be carried out quickly can, and the active material that during a long period of use and should remain in the jacket pipes under shock and vibration loads. A suitable one Material consists of a non-woven wadding (or fleece) made of alkali-resistant Fibers, for example nylon or glass fibers with a thickness of 0.5 to 0.7 mm and a face of 120 to 160 g / cm2. This material has no perforation, but relates 3 a porosity from the different jaws between the fibers, that it's made of, b @ $ t @ h9n. It is permeable to nitrogen (as described below) of 8.0 liters / cm2 / min and a water permeability (as described below) of 1.5 liters; ' cm2 / min.

In general, it is preferred to use a material with a nitrogen permeability in the range from 0.5 to 20, in particular 1 10, and particularly preferred 3 to 9 liters / cm2 / min use. Preferably owns this Material has a water permeability of at least 0.01, in particular 0.1 or 0.5 to 1, 2 or 5, titer / cm2 / min or more.

Depending on the specific accumulator to be manufactured, it can be be any active material. Although the invention in connection with alkaline Nic'Kel cadmium batteries is described, the teaching of the invention, which describes the requirements for the active mass and the material for the coating, thereby reaching a filtration fill and a bed of active material from the bottom the casing (the upper end in use) is built up, also on other electrochemical ones Systems find application.

The casing pipes are preferably clamped at the upper and lower ends in such a way that that liquid can escape from the entire surface of the casing pipes.

Preferably a supply of the sludge becomes continuous during filling mixed, while a small part of the sludge supply from this continuously mixed supply is filled into the casing pipes. The sludge supply is preferred promoted by a pump, which ensures a uniform delivery and the state of suspension of the mud. During the pauses between the filling of the tube plates the sludge is moved from the outlet end to the inlet end of the pump, for example via a Circulation line, circulated. This circulation line is with the pump outlet and a agitated storage tank connected, from which a feed line leads to the pump inlet.

In a first embodiment of the method, the sludge is through a pump fed into a tubular plate. When the plate is filled, it takes place a continuous circulation from pump outlet to pump inlet, followed by the feed of the sludge is carried out into another tube plate.

The apparatus for performing the method of the invention includes preferably at least one filling station with devices for holding the casing a plate resting on the conductive element in a substantially vertical plane is arranged, and a filling distributor device for Einspei solution of sludge in the envelope of a plate which is arranged in this holder, and further a sludge storage tank with stirring devices for receiving a supply of active Material sludge, and dispensing devices for dispensing the sludge from the storage tank to the distribution device of a selected filling station.

The delivery devices preferably contain circulation devices to circulate the sludge to the storage tank when the sludge is not at a filling station is delivered.

The dispensing devices can be a pump with a supply line, which is connected to the storage tank and contains valve devices, a recirculation valve communicating with the pump outlet, sludge from the pump outlet, preferably selectively, to a filling station, or if more than a filling station is used, leads to a selected filling station, or circulates the sludge to the storage tank.

The devices for holding the plates are preferably for Bracket formed by tubular plates and contain a frame that is firmly attached to the filling manifold is connected and upper and lower gripping jaws for includes reversible clamping of the panels to the frame.

The gripping jaws can be toothed and the outer Oberflal chenprofil the top and bottom of the tube plate to be adapted.

At least the upper gripping jaw is preferably provided with an elastic toe, sealing covering provided.

The distribution device is preferably the use of tubular plates adapted and then preferably has an outlet nozzle arrangement consisting of Rigid filling tubes, which are arranged in a straight line at a bosttmmtem distance are, wherein the filling tubes are centered with respect to the jacket tubes of the plate and have outer diameters that are the same as the inner diameters of the plate tubes Thus, the tubes are preferably in a vertical arrangement, so that the sludge can be poured in at the top of the tubes.

The filling tubes can pass through an elastic seal, the dimensions of the frame in relation to the plate are adjusted so that the end of the plate is inevitably pressed against or into the seal to aie To fix the plate in the bracket.

Preferably a pressure sensitive valve is in cooperation with the inlet side of each filler manifold.

Preferably there are at least two per pump and sludge storage tank Filling stations are provided, the circulation valve being a three-way valve acts.

The or each pressure sensitive valve may be arranged so that an automatic changeover of the circulation valve or of the valve devices that connect the or each distribution device to the common feed line, takes place on circulation position, and to a pressure relief of the plate to bring about as soon as the specified pressure value is reached.

The pump preferably consists of those equipped as a single-thread screw Rotor, which is arranged in a cylindrical housing, which is designed as a two-pitch screw thread Eats formed, the screw of the housing twice the pitch as the rotor screw owns. The rotor rotates on its own axis in one direction, while the Axis of the rotor around the axis of the cylinder housing at the same speed, However opposite direction of rotation, circling.

The method of the invention is not limited to the filling of tubular Plates limited. Coverings of other shapes can also be used, for example envelope-like wrappings, and in this case the grid needs do not have the shape of a pen comb; it can rather be a conventional one cast grid or around a net-like grid, for example an extended one Metal grid or around a flat material or a plate with punched openings Act. Even the use of a solid plate would be possible if the required one Electricity storage function is guaranteed to a sufficient extent.

The envelope can be flexible or rigid or stiff Trade material. At least in the case where the envelope is flexible, it will be preferably, a support using porous support means during the filling process genes, for example by means of rigid, porous flat materials, sieves or grids make so that the plate remains aligned essentially parallel, while liquid comes out.

With this arrangement, the introduction manifold must also be modified that instead of a series of tubes that go into the ends of each jacket tube fitted to the envelope, a single or double tubular incision or slot is provided for fitting into the open lower end of the envelope. A double slot arrangement that nests over the end of the grid and providing a pair of slots along both sides of the grating and bracing them therewith can have advantages over a single slot arrangement.

The end of the casing can be lengthened with a after filling Bottom rod to be closed. This can consist of a ren ren tenon, which is the end of the grille engages, and an external one Brace or an integral jaw exist on the pin to grab the outside of the envelope and hold it against the To hold tenons.

In a further embodiment, instead of an inlet manifold of fixed tube outlet openings or fixed slots or incisions an arrangement of retractable filling tubes that extend down into the envelope extend, can be used. With this arrangement one begins so that the Filling tube in full length down into the envelope on the souls extend (which do not have to have centering ribs here, as the filling tubes have these Function). When the active material leaks from the ends of the tubes, the tubes are pulled out along the envelope, finally at the top open End of the wrapping stopped where they can be momentarily clamped, and then taken away to finish filling the plate.

Obviously this arrangement is more complicated than that Arrangement in which the sludge is simply fed into the upper ends of the tube. This simple arrangement is therefore particularly preferred.

The invention is described below with reference to the drawings, which represent preferred embodiments of the invention.

They show: FIG. 1 a schematic side view of an inventive Device, Figure 2 is an enlarged schematic perspective view of the in 1, FIG. 3 shows a schematic partial view of the filling box shown in FIG shown lower jaw in the open position, with only some plate tubes are shown, Figure 4 is a cross-sectional view along the line IV-IV of the Figure 3, Figure 5 is a partial cross-sectional view of the upper Gripping jaws in the open position, as in Figure 3, Figure 6 a general front view of the rotary vane viscometer, which is used to measure the viscosity of the sludge used according to the invention, Figure 7 is a front detailed view of the wing arrangement of the viscometer of the figure 6, FIG. 8 a plan view of the container for use with the viscometer of FIG. 6 for receiving the sample whose viscosity is to be measured, FIG 9 is a top plan view, in optical photomicrograph form, of a nonwoven fabric Material resp.

Fleece, NW, used in the examples and below is described, FIG. 10, similar to FIG. 2, shows a modified arrangement of the arrangement shown in FIG 2 with a feed device provided with a valve and a compressed air stirring device in the distributor, FIGS. 11 to 13 are schematic Enlarged views of a preferred diffuser assembly for the outlet end of the compressed air hose shown in FIG. 10, FIG. 11 being a side view Figure 12 is an end view and Figure 13 is a perspective view of the diffuser from the outlet end, and Figure 14 is a partial schematic view of the manifold and the air hose 210 detailing the relative arrangements.

Figures 1 to 5 show a preferred filling device for implementation of the invention, which allows the panels to operate essentially under gravity to be filled and it then allows the back pressure in the sludge feed to the To let the distributor rise, so that it is possible to increase the filling weight Way to control.

Figures 6 to 8 describe the rotary vane viscometer, i ur determination of the yiskositate properties of the used according to the invention Serves sludge.

FIG. 9 shows the jacket tube material preferably used according to the invention.

Figures 10 to 13 show that used for the following examples modified device.

First, the description of the device of FIGS. 1 to is given 5, since the distributor shown in these figures in the device of FIGS to 13 is used.

The device consists of a sludge tank 10, in which the in the Plate tube to be filled mud is kept.

The tank is equipped with a stirring blade 11 at the bottom of the tank, that by means of belt 12 from a motor 13 with adjustable speed, for Example with 30 to 70 rpm, driven to keep the solids in suspension to keep. A vertical feed pipe 15 leads from a point immediately above of the agitator blade 11 to the inlet opening of a feed pump 16, which is also by means of Drive belt 17 is driven by a motor 13 with adjustable speed. The outlet of the pump 16 is via a vertically downward conveying tube 19 connected to a plate filling station 20. The delivery pipe 19 leads over a pressure gauge 22, a two-way valve 23 and a fishtail manifold 24. The valve 23 can be placed so that the mud is vertically down towards the station 20 flows. In another position, the sludge is circulated via a circulation line 26, which extends down to a point immediately above the agitator blade 11, fed back into the tank 10. The lines 15 and 26 preferably have the same cross section.

The mass of the sludge supply is preferably about 15) kg, for Example about 100 to 200 kg, held. The fed into each tube plate Mud, the individual filling weight, is in the range of 400 up to 1000 g. In general, the weight ratio of active material to the Example 75 kg, in the continuously mixed sludge supply, to the individual Fill weight in the range from 1300: 1 to 25: 1, preferably 1000: 1 to 200: 1 and in particular 160: 1 to 100: 1.

The station 20 consists of a frame 29 which, with reference to the Manifold 24 is rigidly attached and has upper and lower gripping jaws 30 and 31.

The gripping jaws 30 and 31 are toothed and correspond to the outer one Surface profile of the lower and upper ends of the tubular plate as the plate into the gripping jaws with their open lower end facing the distributor 24 will. The manifold has an outlet nozzle assembly made up of 6.4 mm long copper tubing or other stiff esophagus, the outer diameter being the inner Correspond to the diameters of the plate tubes. These esophagus are in some way Spaced from each other in a straight line, each with the center of the The esophagus is aligned with the center of the plate tube.

Thus, the open ends of the plate tubes are fitted to the Esophagus are put on and are in this state by the upper jaws 30 held, which can be equipped with an elastic sealing lining.

The lower jaw 31 holds the plate in position and presses the Tubes against a thickened end portion of the conductor pins or ellen. the Areas of the plate are completely free.

The souls are made of a suitable metal alloy, possess a conventional structure and are arranged on a guide rod so that their Centers correspond to the centers of the tubes with which they will be used. the Cores are preferably equipped with short axial ribs as spacers, those for centering the souls in the jacket pipes serve and a Prevent the souls from bending during handling prior to filling.

The station 20 is detailed below with reference to the figures 2 to 5 described.

As stated above, the station 20 includes a frame 29, which is rigidly attached in relation to the manifold 24.

This frame consists of two parts 32 and 33 that oppose each other are pivotally connected to each other around the left edge.

The part 33 is rigidly connected to the distributor 24. The top and the lower jaws each consist of two parts 30 A and 30 B as well as 31 A. and 31 3. The parts 30 A and 31 A are from the movable part 32 of the frame 29 supported, and the parts 30B and 31B are from the fixed part 33 of the frame 29 worn.

The fixed part 33 supports the upper and lower at the same time Lock levers 36 and 37, which are arranged so that they in the upper and lower Handle 38 and 39 of the movable frame part 32 engage and so the filling station conclude.

The fixed part 33 of the frame 29 also supports a lower support rod 42 a recess 43 through which the flag 44 of a plate 45 passes, and which at the same time facilitates the insertion of the plate in the filling station.

The upper and lower gripping jaws 30 and 31 have toothed profiles, which correspond to the outer envelope dimensions of the plate, and the two parts of each When closed, gripping jaws delimit a series of cylindrical holes 48, which are connected to one another by cavities 49. These cavities 49 have twice the thickness of the material 47 of the envelope, so that cutting or Crushing of the envelope is prevented by the gripping jaws.

The lower gripping jaw 31 presses the fabric or fleece 47 of the Wrapping against the broadened shoulders 51 of the souls en 52 of the plate, so that a good one Let tightness guaranteed (compare Figures 3 and 4).

FIG. 5 shows the casing pipes used in the distributor 24.

A manifold plate 54 has a number of feed pipe surfaces 55 going down through them with tapered ends 56 going through openings in a rubber seal 58 hindurc ': q guide. This seal is elastic and can with the fingers: n only up to about half of the uncompressed starting thickness, @@ e is about 3.2 mm, are pressed together. Figure 5 zip: the sheath 50 in position Chen over the ends 56 of the ZUleitungsröhr. In fact, however, the arrangement is so that the; i, device 58 by the forcibly inserted sheath 50 to about 1.6 mm must be compressed in order to place the guide rod 1 -r,, te on the support rod 42 of the frame to bring. (This @@@ sion is not shown in the drawing). The cheeks; presses the fabric or fleece 47 (Fig. 4) of the envelope around the ends 56 of the Feed tube 55, so that you can achieve a good DiKt-g speed at the upper end.

The pump 16 is one under the trade name Monopump known pump, which ensures a uniform supply and discharge and a single-start screw equipped rotor, which in a cylindrical Housing is arranged, which is designed as a two-start screw thread, wherein the screw of the housing has twice the pitch of the rotor screw. Of the The rotor rotates on its own axis in one direction, while the axis of the Rotor around the axis of the cylinder housing with the same speed, but opposite Direction of rotation, circling. Using this pump gives a positive one Delivery rate at a steady flow, with the separation of liquid or Solids in the sludge is prevented.

In another embodiment (not shown) is the filling station 20 designed as a twin distributor arrangement, being each distributor is fed by the pump 16. The two-way valve 23 is a three-way valve replaced, and each line leading from the valve 23 to a manifold contains a pressure sensitive valve 70.

This valve 70 is preferably a pressure reducing valve, which can be adjusted to any desired pressure, for example 1.05 kg / cm². If this value is reached, the valve maintains the pressure at 1.05 kg / cm2 as long as until actuation, for example manually, takes place.

The procedure would then be to insert a plate into a Manifold uses and the valve 23 either from the circulation or the other Manifold moves. After the plate has been filled, for example in 5 seconds, it is left the pressure increase to 1.05 kg / cm2 and then hold at this value for 5 seconds.

During this time the filled plate is removed from the other distributor removed and replaced with a new plate. The valve 23 can be switched over to this so that either a temporary agitation or immediate filling of the new record takes place.

In a further embodiment, the pressure reducing valve is 70 arranged so that a circulation of the pump supply and a pressure release with respect to the plate takes place once the set pressure is reached.

During operation, the filling process takes place as follows: The sludge is prepared in the tank 10 by means of a stirring blade 11 to the desired composition. Then a tube plate 50 (45 in Fig. 2) is oriented so that the tubes of material 47 are located over the metal cores 52, and against the jaws 30 B and 31 B in the Station 20 is placed with the open, lower ends facing up against the seal 58 and over the ends 56 of the feed tube 55 of the manifold 24. After closing the part 32 of the frame, the jaws 30 and 31 are closed has, the Lock lever 36 and 37 over the handles 38 and 39 laid. While the stirring blade 11 is kept in operation, the valve 23 is open Brought circulation position, whereby the pump 16 is connected to the pipe 26. After this one has switched on the pump 16, is circulated until a steady flow is reached. During the circulation, the pressure gauge 22 shows the pressure value zero at.

Then the valve 23 is operated so that the pump 16 with the manifold 24 is connected. The sludge enters station 20, with the active material fills the inside of the jacket pipes. The valve 23 is in this position held until the jacket pipes are filled with active material.

At this point the pressure gauge shows a relatively sudden one Pressure increase. When the pressure has reached the desired switch-off value, the valve 23 is operated so that the sludge via the pipe 26 into the tank 10 is returned.

After opening the jaws 30 and 31, the filled plate removed and further processing steps, such as introduction of the bottom rod, soaking (soaking), drying and electrolytic formation.

The excess sludge contained in the manifold falls into the Tank 10.

In the case of continuous operation, the indicated by the pressure gauge 22 can Pressure increase can be used to control the filling cycle, for example for Actuate valve 23, open jaws 30 and 31 to release manifold 24 and attaching a new panel in a clamped arrangement.

Limit switches could be provided in such a way that they are replaced by the new Plate, causing manifold 24 to open valve 23 in To reset the filling position.

Below is that shown in Figures 10-14 contraption described.

The device shown in FIG. 10 is a simplified version of the device of Figure 1, with no facilities for the continuous stirring of the sludge and the circulation of the sludge passing through the walls of the tubular envelope passed through, and no devices are designed to apply a certain pressure to the sludge feed, after the jacket tubes have been filled with the mud under gravity.

In this arrangement, the sludge is supplied from a calibrated Tank 200, which is arranged above the distributor 24 and connected to this via a feed line 201, a valve 202, a Y-shaped connector 203 and another feed line 204 is connected, the line 201, the valve 202 and the line 204 so are arranged vertically as far as possible.

The sludge is thus in the distributor under gravity under one hydrostatic pressure of about 18 to 36 inches. For standardization of the hydrostatic pressure, the sludge in the tank 200 is preferably up to the same height of about 76.2 cm above the inlet height 205 of the plates.

The tank 200 has the shape of a cylinder that is attached to a tight seated plastic funnel 206, the end 207 of which protrudes into the line 201, is equipped. This prevents solids from settling in tank 200; at the same time they can through an air hose 218, the end of which is located directly located above the outlet end 207 of the funnel 206, be gently stirred.

The other leg 208 of the Y-piece 203 has a valve 209 connected, through the water to rinse the manifold in use can be directed. A Compressed air hose 210 leads through a Plug 211, which seals the interior of the leg 208 movably. The hose 210 can be moved back and forth about 2.5 to 10.2 cm in plug 211 without that thereby the sealing of the leg 208 is impaired. The hose 210 also leads down through valve 209 and line 204 into the manifold 24.

The end 215 of the tube 210 is about 1.3 to 2.5 cm in use above the inlet level 205 of the plate.

This air hose arrangement was not used for the examples 1 to 7. In Examples 8 to 14, where it was used, one is observed more even filling. When using (Examples 15 to 23) in the figures 11 to 13, a modified outlet piece 216 is obtained which is very uniform Filling.

Figure 14 shows a partial view of the arrangement of the compressed air hose 210 in manifold 24. The inner diameter of the inlet pipe leading to manifold 24 220 is about 20 to 25 mm.

It was found to match those used in Examples 1-23 Slurries an air velocity of about 3 to 12, preferably 5 to 10 and especially about 7 liters / min with the modified outlet piece 216 to an excellent one Distribution of the sludge in the jacket pipes results when the hose 215 is in vertically above the central tube and about 1.3 to 2.5 cm away from it is located. Particularly good results are obtained when the hose is between these Positions "oscillated" about 1 time every 1 to 5 seconds. The fishtail housing of the distributor 24 (Figure 10) is about 25 mm deep and, from point 221 or 220 to to inlet level 205, about 100 mm high. The width at the inlet level is 205 about 15 cm. The internal volume of the distributor 24 is thus approximately 260 ml.

The manufacture of the modified one shown in Figures 11-14 Outlet piece 216 is accomplished by melting and squeezing the end 215 of the Hose 210, for example by means of a vice, to a length of about 7 mm. After cutting off the end of the flattened piece, the outwardly standing ears cut so that a pair of tabs 225, 226 with a End slot 227 and angled side slots 228 and 229 are formed. In this way A fan-like layer of air emerges from these openings.

In addition, in order to achieve lateral agitation, there are holes 230 about 0.5 mm in diameter in the cylindrical, non-flattened part of the tube 215 about 7 mm from the end of the flattened part. From these Holes emerge air streams 231 radially. Additionally there is a pair of Holes 232, also about 0.5 mm in diameter, in the inclined area of the tube between the flattened and non-flattened part. Step out of these holes Air currents 233 down towards the flattened end, at an angle of about 30 inclined to 60 ° relative to the longitudinal axis of the tube 210.

Below is the device shown in Figures 15 and 16 described.

The device of FIG. 15 is the device shown in FIG similar, but includes means for feeding compressed air into the manifold 24, in a similar manner to that shown in FIG. 10 using a hose 210 is shown for feeding an outlet end 215 located in the manifold 24.

Identical parts have been given the same reference numbers.

The sludge is pumped by a pump 16 in the same way as in Figure 1 described, conveyed to the filling station 20, the only difference in the Agitation of the sludge in the tank 10 consists of a perforated air hose 250 which extends around the bottom inner surface of the tank and by an air line 251 is supplied with air. In addition to this air circulation takes place using a propeller stirrer (not shown).

It finds the same distributor 24 and the same filling station as described in Figure 10, use.

The compressed air supply and the stirring are carried out through an air line 252, stirring via a valve 253, a pressure meter 254 and a flow meter 255; the introduction of compressed air via a valve 256, a pressure meter 257, a flow meter 258 and a shut-off valve 259.

The end 215 of the hose 210 is as a copper tube of about Shaped 4.8mm in outer diameter and approximately 51mm long.

It is on a slightly enlarged scale in Figure 16 in the orientation in which it is located in the distributor. It's at an angle of about 45 O to the vertical, with the three holes 260 facing up in a vertical Level.

The invention relates generally to new alkaline accumulator electrodes, Cells containing these electrodes as well as alkaline cells made from these cells Accumulators.

Thus, in a further aspect, the invention relates to ene alkaline battery electrode, which is characterized by a porous coating, die'in particulate active material included, the under alkaline Conditions is electrochemically active, the porous envelope from an aqueous Active material sludge containing 0.5 part of active material per part of water, able to filter out a bed of active material.

The electrode preferably has one or more internal current-conducting ones Elements that are connected to an external current conductor for the plate. Some suitable forms of such conductive elements are already above described.

In an alternative embodiment for an internal conductive Element is a wound r) wire spiral, with the outer diameter the spiral is the same size or a little less (for example 80 to 100 t '), than the inner diameter of the casing when a casing is used becomes, or slightly less than the inner diameter of the pocket, if a flat, pocket-shaped envelope is used. Thus, in general, that conductive element in this arrangement both the conductive function as also take over the support function of the envelope.

Accordingly, the arrangement can be made in any manner, provided that at least the first function, preferably both functions, are fulfilled.

Instead of a spiral, zigzag arrangements can also be used. The ratio of the pitch of the spiral or helix to its is preferably outer diameter about 1: 1, for example 0.5: 1 to 2 or 3: 1.

In an alternative embodiment, one or more electrically conductive Elements that lie outside the porous envelope and preferably surround it, be used.

In some cases, the porous envelope must itself with sufficient Electricity can be equipped. In this case it can be for example around a metal screen or mesh made of non-woven material such as steel wool, or be a metallized, non-metallic material. One can use the power line also by impregnation with a conductive particulate material, for example Graphite.

The following is a preferred example of a metallized test non-metallic Material specified.

It preferably has an air permeability of about II x 10 Liters / m2 / sec, which is determined as follows: After getting a sample with a 6.16 cm cross-sectional area is firmly clamped, the time for the flow through will be of 10 liters of dry air through the sample at 200C and a pressure difference of 1000 mm water column measured.

The material preferably weighs from 0.01 to 0.20, for example from 0.07 to 0.10 g / cm2 and is 1 to 3 mm, for example 2.5 mm thick.

It is preferably a needled two-component material made of alkali-resistant fibers, for example nylon fibers.

The fibers generally have an individual length of well over 500 u and are typically 1 to 3 cm long with diameters of 20 to 30. the Fibers are preferably not subjected to any melting or softening process, and thus the fibers are not fused together.

The fibers have substantial areas of coatings along their long sides although these need not be complete coatings. Preferably there are also accumulations of material at or adjacent to the intersection points.

These coatings and clusters can be made of any suitable conductive material Material, for example made of metal, for example nickel. The material contains preferably about 0.01 to 0.20, for example 0.05, g metal / cm2. The production of the fabric can be done in such a way that a mat made of two-component fibers is used for Example after the air lay-up or carding process, and then forms the mat of the Subjects needling to tangle the fibers.

The porous envelope can be a non-metallic, alkali-resistant one Material, for example a non-woven material. This is preferred below material described and labeled NW. However, the envelope can also be in two parts be, with an outer, strength-giving, coarsely porous, for example perforated, container and an inner, fine-permeable filtration layer available.

The two layers are optionally bonded together, either by a permanent or a reversible connection, for example by means of a water- or alkali-soluble glue.

The outer container is preferably metallic so that it is the active one Keep material, especially in the positive plate, in a tightly compressed form able.

When the filtration layer is made non-conductive or not is inherently conductive, it is preferred to have one or more internal current-taking Elements to use.

The following is a specific example of such a shape of the electrode specified.

The outer container consists of a flat housing made of a perforated Steel sieve that is open at the top and bottom. The perforations have an extension of at least 02, for example 0.25 or 0.38 to 0.50 or 0.75 imin. In the case there is a glass barrel filter liner, preferably with permeability in the order of magnitude described above.

The inner conductive element is a pressed one or stamped metal comb or a perforated metal plate, for example made of Steel or lead, which can be nickel-coated. When using lead, the Manufacturing can also be done by casting.

The element preferably has shoulders at the top and bottom as well as tabs, which extend beyond each end and are arranged to pass through Slots of plastic end plugs, see B. made of nylon, guide the force-fit sit in the ends of the netall housing.

The flaps are then bent over, which means that the casing is held together. There is also an end conductor on the ridge, which is extends upward through the 'connector at the top. The bottom end of the element may have ears that extend outward sideways and into slots engage the end of the metal housing so that the element during the filling process is centered.

The housing can be from the open bottom end, as above for tubular plates described, filled. Then the ground plug is inserted. It can a slotted fill head as described above can be used.

The housing can be assembled in a continuous process by placing a continuous layer of the filter material on top of a Applies the front surface of the metal container, then folds the housing to form, as coherent pipe, this is welded and then brought to the desired length.

In a further variant of the process, the sludge is supplied from a built-in pressure storage tank equipped with a valve Sludge inlet and a valve equipped compressed air supply line is. There can be two or more such feed containers, which through Valved lines connected to a common feed to the manifold are, so that if necessary layers of different composition in certain Consequence can be deposited in the jacket pipes, for example active material layers, followed by layers with higher concentrations of conductive material such as graphite. Such an arrangement would allow the sludge to be removed without the use of a Pump can be fed that can wear out in contact with the mud, and could also be used to build up the pressure to the desired value in the sludge supply or the sludge supply.

In another variant there is still a pair more impermeable Plates that adapt to the outer profiles of the covered casing pipes, provided in such a way that that they can be clamped over the plates and then quickly removed again. These plates have vent openings at their lower ends. This can proceed in such a way that the jacket pipes are partially filled, then the impermeable ones Brackets or plates attached and finally lets the air pressure rise to the bed partially created by compressing the solids into a compact one Compress bed at the bottom of the jacket pipe, with the liquid flowing through the vents in the un or.

exit. This sequence of partial filling, clamping and compaction can be repeated at any frequency until the plates are filled are.

In a further variant of the filtration filling process, a diffuse inflow of air or gas into the interior of the manifold to remove the To reduce settling of solids before entering the wrapped panels. Preferably the air flow is in the range of 2 to 15 liters / min for a tube with a diameter of 0.5 cm. The air stream preferably has flow components that at an angle of at least 30 °, preferably 60 to 90 °, to the longitudinal axis of the Main air flow exit.

The examples illustrate the invention.

E xample 1 through 23 These examples describe certain Plate making methods using those shown in Figures 10-14 Contraption.

There are positive plates with 15 jacket pipes of 36.9 cm each Length used. The jacket pipes are made of non-woven polyethylene terephthalate fibers; in practice, however, alkali-resistant fibers such as nylon or glass fibers, be used. This alkali-resistant material possesses preferably the same properties as the polyester material used in these examples. This polyester material is made as follows: A thin layer (1.5 m wide) made of fibers with an average length of 11.4 cm is made using the crimping technique manufactured. Then about 10 layers are placed on top of one another so that an endless non-woven Fleece (also 1.5 m wide) is created.

The fibers generally extend longitudinally in the Non-woven material that is folded in a zigzag pattern when it is moved by a conveyor belt, that in the longitudinal direction of the fleece material on a band running at right angles thereto runs in, is removed. Thus the fibers extend substantially transversely to the longitudinal direction of the fleece material, due to the running direction of the second belt however, the fibers in adjacent layers are opposite at a small angle inclined to the transverse direction.

The material obtained is then impregnated with a Subject to so-called weight percent polyacrylic resin binder. It has a thickness from 0.5 to 0.7 mm and weighs 120 to 2160 g / cm This material then becomes a Jacket pipe assembly processed by putting two layers of the material through one Multiple sewing machine runs to cut the layers along parallel lines (for example at a distance of about 25 mm) to be connected to each other. Here arise bags or

Tube.

Then the material is dipped in a phenolic resin and then dried. The phenolic resin absorption is about 30 percent, based on the dry weight of the non-woven material.

After cutting to length, mandrels are made with a circular cross-section 7.3 mm in diameter inserted between the rows of stitches to form the pockets. The material has an air permeability of cm liters / min / cm and a water permeability of 2 permeability of 1.5 liters / min / cm. Its structure goes out figure 9 emerges.

Figure 9 shows that this nonwoven material from statistically tangled consists of individual fibers. The fibers have a diameter of about 25 Bu, the range generally being from 20 to 50 p. The gaps between each Fibers generally have a size of less than 250 / u, mostly less than 100 each.

In addition, the material has a thickness of 0.5 to 0.7 mm a three-dimensional structure that results in the overlapping of numerous individual fibers any passage, from one side to the other, allowed through the fleece material.

The measurement of the air permeability is done as follows: One One Sample 2.8 cm in diameter (6.16 cm effective cross-sectional area) is placed in position clinged. Then the time required for the passage of 50 liters of dry water is measured Nitrogen through the sample at 20 ° C. with a pressure difference of 1.5 cm water column is needed.

Because of the high permeability, the material of the measurement is by means of the mercury porosimetry or the air flow through a saturated with alcohol Sample not accessible.

The measurement of the water permeability is done in such a way that the time is measured which initially needs a 42 cm high water column with a volume of 1 liter to flow through the sample under gravity.

After having shielded the bottom of the column under the sample water is fed above the sample, and then the lower end is below the sample is open to the atmosphere. This material is in the following Tables II A through II E referred to as nonwoven, NW.

The inner volume of the encased panels, which are encased with Y-casing pipes are, i.e. the volume that can be filled with active material, is 180 ml.

In the case of another material, provided that it is alkali-resistant is, it is a spun-woven material that is air permeable of 6.0 liters / cm2 / min. It contains 17 weft threads / cm and 22 warp threads / cm. The warp threads have a diameter of about 250 », and the weft threads one Diameter of about 375. Microscopic examination shows that the gaps between adjacent warp threads and adjacent weft threads a maximum of about 250 x 250 M be. However, these gaps are crossed by numerous loose fibers, protruding from the threads.

Examples 1 to 7 For Examples 1 to 7, this is found below procedure described application.

The air hose 210 is not used.

In Examples 2 and 3, the hose 208 is removed. The funnel 206 is not used, and a tight-fitting rubber piston is on the top of the container 200 and used there to additionally sludge into the plates after they have been filled under gravity.

The Y-piece 203 is made by a direct connection of the line 204 replaced with valve 202.

After getting the mud prepared and placed in a closed container has shaken thoroughly, a sample is made for sedimentation and viscosity measurements retained. After you get out of the aforementioned tubular casing and conventional Lead grids (used in these examples for ease of access) a has made covered, provided with conductor pins plate, this is in the arranged for this purpose. After closing valve 202, the sludge is poured into the tank 200 to the standard level, and immediately the valve 202 is then opened.

By pouring the well-shaken sludge into the container the turbulence generated will mostly be the solids in suspension held. The sludge flows down into the casing pipes to the bottom of the casing pipes opposite the rod 43, where spontaneously liquid from the jacket pipes in the form of large Droplets emerge as the solids level inside increases of the jacket pipes converge towards the inlet opening. This filling scheme, which is available as a Filtration filling is designated, is designated in Tables II A to II E with "B". In certain other examples, namely example len 4, 5 and 6, loses the sludge already water as it enters the upper end of the jacket pipes and strides then proceed to the bottom of the jacket pipes. This filling scheme is called injection filling or press filling and is represented by A in the tables. These The type of filling occurs preferentially with sludges that have larger solid / liquid ratios own; other work with particulate slurries has found that Sludge with rotating vane viscometer torque values (according to the given here Definition) of less than 0.83 m. g (0.006 lbs. ft) at 20 ° C for filtration fill (B) tend, while above this torque value, a propensity for injection filling (A) exists. Furthermore, it was found that with the A-filling the particles tend to to settle in the area of the inlet end of the jacket tube.

The plate is then removed and weighed, taking the weight of the active material in the jacket pipes receives (the dry weight the lead grid and the jacket pipe casing are known). After marking the plate and inserting a polyethylene base, the plate is dried at 70 ° C. for 24 hours.

After the selected panels have been cut, the cut ones are cut Parts weighed (see Table III and the remarks on this).

In some cases, not all casing pipes have a fill a. The reason for this is a clogging of the nozzles or esophagus 55 (Figure 5) in the distributor by large Active material particles.

It has been found that it is best to use the container 200, the conduit 201 and the valve 202 to drain after each attempt and the system with Water, both down through tank 200 and up through the nozzles Rinse 55.

In those cases, namely Examples 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 19 and 23, where the casing pipes by the first "gravity filling" are not filled at all, the device is, as described above, flushed. After adding another standard volume to the plates, are some of the remaining empty casing pipes are generally filled. These examples are marked with "A" for the first filling pass, t'B "for the second filling pass on the same plate and "C" for the third filling process on the same plate, and so on.

The results for these examples are in Tables I A and I. B compiled; the viscosities of the slurries used are given in Table III and the results for the layering of the active material in the jacket pipes are listed in Table IV.

The active materials used are marked with negative, "" positive 1 "and positive 2".

"Negative" means a conventional negative alkaline active Material containing 76 percent by weight cadmium hydroxide (Cd (OH) 2), 5 percent cadmium, 15 Percent iron oxide (Fe203), 2 percent graphite and 2 percent paraffin. According to According to the sieve analysis, this material has the following grain size distribution: Test sieve BS 410 normal (mesh) P percent by weight> 16> 1000 0 <16 100 <22 < 699 98 4 30 <500 94 <60 <250 82 <100 <150 64 <350 <45 42 Positive 1 "is a conventional positive alkaline active Material that is 85 percent by weight nickel hydroxide (Ni (OH) 2) and 15 percent graphite in powder and flake form (powder: graphite = 66:34).

The larger particles of flake raphite have been found to be light lead to more frequent blocking or clogging of the plates. By using the The sample is subjected to sieving to remove at least a major portion of the material with a Removing particle sizes below 40 mesh can correct this problem.

"Positive 2" is this partially sieved sample, which has the following particle size distribution according to the sieve analysis: Test sieve BS 410 normal (mesh), u percent by weight> 16> 1000 0 <16 1000 100 <22 <699 100 <30 <500 100 <60 <250 97 <100 <150 86 <150 < 105 77 <350 <45 50 The visual inspection of the sieve fractions shows that the coarsest fraction consists of graphite flakes with a diameter of 1 to 2 mm.

Visual inspection of the positive 2 material shows that it is still a significant one Share of graphite flakes is present, which under normal daylight unarmed eye (20/20) are visible.

B e i 9 p i e l e 8 b i 5 23 The following applies to these examples specified filling method application.

The device of FIG. 14 is used for Examples 15 to 23.

The sludge is shaken thoroughly in a sealed container; a sample is retained for sedimentation and viscosity measurements. After this one has closed the valve 202, the air line 208 with an outlet opening, as described for outlet piece 216, to a flow rate of 7 liters / min set. Then the LeiturE 204 and the distributor 24 (Figure 10) rinsed with water.

After you have clamped a plate, the air hose is through the valve 209 is inserted so that its end 215 is arranged as in Figure 14 shown. The stopper 211 is then put on. This is where the air duct 210 with a straight or smoothly cut outlet opening in the examples 8-14 and with the outlet end 216 in Examples 15-23 at a flow rate operated from 7 liters / min.

After the shaken mud is poured into the container 200 quickly valve 202 is opened and air line 210 is closed approximately once every two up to 3 seconds over a vertical section of about 17 to 25 mm up and down respectively.

oscillates.

The casing pipes are filled with the sludge after the B filling or filtration filling. In certain examples, namely Examples 8, 9, 10, 11, 13, 14, 16, 19 and 32, some casing pipes will not work on the first pass filled. Therefore, as in Examples 2 to 7, the plate is removed from the manifold removed. After flushing the manifold, the passage with the partial filled plate repeatedly.

In some other examples, namely 16 and 20-23, the Air pressure from line 210 to compress the active material in the jacket tubes used.

This is done as follows: When there is no more sludge from the casing pipe material runs out, additional sludge is poured into the container 200 if necessary. Then the valve 202 is closed and the plug 211 is held in place.

This prevents water droplets and sludge from escaping from the top half of the plate causes; the air pressure is allowed to rise until the Seal on the upper jaw 30 venting takes place. Then the upper End of container 200 covered but not tightly closed and valve 202 is opened to bring about a pressure release with the atmosphere and at the same time to stir the sludge in container 200. The valve 202 then operates for a few seconds opened to feed more sludge into manifold 24 and then closed again. The pressure is then allowed to rise again until there is a vent around the upper gripper jaw seal takes place around. This sequence of procedures is repeated several times until there are no more Liquid can be squeezed out of the plate, but only air is pushed through the porous active material and the jacket tube material, as is to be recognized by the presence of water bubbles on the surface of the plate gives.

A number of slurries are made. The details regarding Composition, viscosity, sedimentation and suspension half-life are in Table I compiled.

Comments on Tables I, II A to II D. III and IV 1) The Syrnbol t 'means that air pressure was applied to the solids in the plate. For this valve 202 is closed, the pressure is allowed to rise, air is vented and the manifold is left replenished with mud for two such cycles; Al "means that only one cycle was applied.

2) The jacket pipes are numbered 1 to 15, starting at the end of the flag.

2a) Reference is made to the manufacture of pellets in connection with Example 18. If there are small pellets of active material over the open Ends of the casing pipes extend out, this is an indication of a tendency to change the type of infill from type B to type A.

3) The symbol "O" means that the air hose is moving up and down (oscillates).

4) Wet paste in the plate. It becomes the weight x of the jacket pipe, of lead souls and a floor stick. The values given are it is the weight of the wet, filled plate after attaching the bottom rod minus x.

4a) This value is lower than the previous value. This is possible presumably due to the displacement of some water from the wet solids the air pressure back.

5) Settling the sample (percent). This is the height A is the solids in the container divided by the height B of the liquid from the bottom of the container, expressed as a percentage, after thoroughly examining the sample for 0.5 minutes was shaken and then left to stand in a vertical position for 24 hours has been.

The container is a test tube with a round bottom and 1.5 cm inside diameter. The lamb filling is at least 9 cm.

6) Half-life of the suspension. This indicates the time which requires the solids level of the sample in the container, as specified under 5), to descend halfway between B and A.

The test is carried out using a rubber band with the lower Edge at the halfway level, i.e. (B + A) / 2 cm from the bottom of the test tube; orders the reagent bottle to shake vigorously for a period of at least 0.5 minutes or until all solids are removed from the bottom of the test tube, then aligns the test tube and the time from that point to that Measure the point in time when the light is first visible under the rubber band.

7) Layering (Table III). The determination takes place after 24 hours Dry the plates at 70 ° C.

The guide rod and the bottom rod are then cut from the plate; the rest is cut into four equal horizontal strips, namely A, B, C and D, the strip A originating from the lower end of the plate. Then the Strips weighed.

8) Torque values. The rotary vane viscometer readings for some of the sludges used in the above examples are listed in Table I.

The viscometer used is described in FIGS. 6, 7 and 8.

The viscometer consists of a frame 110 with an electric motor 111, which includes an agitation assembly 120 through a gear box 112 and a torque converter 119 drives.

The speed in the gear box 112 is controlled by a tachometer generator 113 scanned, the output line of which is connected to a digital voltmeter 113 A. is. The voltage signal generated by the torque converter is recorded in a recorder 114 fed in, the one with variable running speed and variable scale is equipped.

A sample container 130 is clipped onto an adjustable one Table 115, which is lifted onto guides 116 by means of a pneumatic cylinder 117 and can be lowered.

The sample container 130 has a removable lid 131, which is above the agitator assembly 120 is attached. The lid can be on the container by means of a outer bayonet lock not shown) are attached.

The Psührnordnung 120 is releasable on the output shaft 118 of the gear box 112 attached and consists of a central rod 121 with a protrusion 122 on the lower end which, in use, engages a hole 132 in the bottom of the container 130.

The rod 121 has a diameter D 5 of 1.3 cm and carries three Pairs of stirrers 123, 124 and 125. The stirrers 123 and 125 are located in the same Level, at right angles to stirrers 124. All stirrer blades are oriented vertically and thus parallel to the axis of the rod 121. The stirrer are carried by arms 126, 127 and 128. The distance D 6 from the center of the arm 126 to the projection 122 is 6.5 cm, the distance D 7 from the center of the arm 127 to protrusion 122 3.9 cm, and the distance from the center of arm 128 to the protrusion 122 1.6 cm. The width of each stirrer D 3 is 1.2 cm, with a height D 2 of 1.2 cm and a thickness of 0.1 cm. The distance D 4 from the inside edge of each stirrer to the surface of the rod 121 is 1.5 cm.

The distance D 1 between the outer edges of the stirrers in a stirrer pair is 6.8 cm.

The internal height of the container 130 is 8.2 cm with an internal one 8.8 cm in diameter. There are four inner baffles 135, which at the diameter ends, each at right angles to each other, are arranged. The thickness D 10 of each baffle 135 is 0.30 cm, with these baffles by an amount of D 9 = 0.5 cm protrude inside. The distance D 11 of the guide plates on the diameter is 7.65 cm. Each baffle extends the full height of the container. The container and the baffles are made of smooth, stainless steel.

The use of the device happens as follows: The container is Filled to a depth of 8.2 cm with the material to be tested, in position lifted, clipped to the table 115 and closed with the cover 131.

After the recorder 114 has been operated, the motor 111 is switched on, being by means of the gearbox for a low shear rate, for example 6 rpm.

The output torque and the existing torque are through the torque converter 119 is determined. The engine and driver are operated for so long until a steady torque value is registered for a period of at least 2 minutes has been. This then represents the permanent torque value. This permanent torque is given, and if there has been an initial peak, that fact becomes also anxious. The sample is then removed, shaken, taking the amount of the material is measured and then the container is refilled. Afterward the measurement is repeated at a higher shear rate, for Example of 18 rpm. This cycle is determined by the desired shear rates repeated at will.

The background torque value, that is, that when the container 130 is empty is found is 0.27 g. m (0.002 lbs. ft) below all in Table I. specified shear rates. When the container is filled with water, is the Value 0.27 g. m.

At the rotating vane viscometer torque value defined here it is the value of the continuous torque value of the sample that is specified in in the aforementioned manner by means of the aforementioned device at a shear rate of 6 rpm at room temperature (20 ° C) minus the background value at 20 00. Examination of the plates of Examples 1 to 23 showed the formation electrical energy.

T a b e l l e I Sludge- Used Active Solids Rotary Vane Viscometer Selling half-value characteristic in mate liquid shear torque peak of the pro time the number example rial speed, ment, *) be,% suspen-rpm m. g sion, sec 810002 1, 2, 3 negative 0.34 / 1 6 0.42 no 71 5 24 0.55 42 0.55 810004 4, 5, 16 "0.56 / 1 6 0.42 no 90 -24 0.55 42 0.55 81005 17, 18, 19 "0.46 / 1 6 0.42 no 94 -24 0.42 42 0.55 810006 20, 21 "0.25 / 1 6 0.42 no 58 5 24 0.42 42 0.42 810007 22, 23" 0.75 / 1 6 0.69 24 0.69 42 0.69 *) The base torque value is 0.28 g. m (0.002 1bs. ft); for the determination of measured values, see 2. abs. according to table IV C T a b e l l e I (continued) Sludge-used Active Solids Rotary Vane Viscometer Selling half-value characteristic in mate liquid shear torque peak of the pro time the number example rial speed, ment, *) be,% suspen-rpm m. g sion, sec 810010 6 Positive 1 1/1 6 0.42 yes 50 170 24 0.55 42 0.55 810013 7, 8, 9 "0.75 / 1 6 0.42 yes 57 210 24 0.55 42 0.55 810 015 10, 11, 12 "0.5 / 1 6 0.42 no - -24 0.42 42 0.55 810017 13, 14, 15 Positive 2 0.5 / 1 6 0.42 no 45 150 24 0.42 42 0.42 810001 - Negative 0.96 / 1 -. - not measurable measurable *) The background torque value is 0.28 g. m (0.002 lbs. ft); for the determination of the measured values, see section 2 according to Table IV C T a b e l l e II A At- N = negative tube time the air entered through the plate P1 = positive 1 up to the sludge volume, ml line P2 = positive 2 type filling X straight solids sludge the end liquid identification plate Y diffuse number under sorende gravity O (3) force, sec 810101 1 0.34 / 1 N 810002 NW 5 1000 without filtrate 420 ml, which settle on 30 ml of solids in 1 min 810102 2A 0.34 / 1 N 810002 NW 5 500 without 2B 0.34 / 1 N 810002 NW 5 - without 810103 3A 0.34 / 1 N 810002 NW 8 600 without 3B 0.34 / 1 N 810002 NW - 200 without 3C 0.34 / 1 N 810002 NW - 200 without 4A 0.56 / 1 N 810004 NW 18 250 without At- number of empty jacket tubes (2) Filling type wet paste play wall Passages in the plate for "filling", g P through the plate piston A through air (1) 810101 1 without 1 - B 286 810102 2A without - tube 8 - 15 empty B -2B P1 2 170 810103 3A without 6 tubes empty B 190 3B without all tubes filled B -3C P1 3 some additional sludge B 318 pressed in 4A without 6 tubes empty A - T a b e l l e II B Bei- N = Negative tube time until through the plate air inlet play P1 = positive 1 small filling of the trodden areas, X straight end P2 = positive 2 type plate under slurry volume, Y diffuser end solids Mud gravity, ml O (3) liquid code number sec 4B 0.56 / 1 N 810004 NW 18 150 without 5A 0.56 / 1 N 810004 NW - 600 without 5B 0.56 / 1 N 810004 NW - 225 without 810201 6A 1/1 P1 810010 NW 5 250 -6B 1/1 P1 810010 NW - 225 -6C 1/1 P1 810010 NW - 100 -810202 7A 0.75 / 1 P1 810013 NW 5 400 -7B 0.34 / 1 N 810002 NW - 300 -7C 0.75 / 1 P1 810013 NW - 250 -7D 0.75 / 1 P1 810013 NW - 100 -810203 8A 0.75 / 1 P1 810013 NW 5 1200 X 8B 0.75 / 1 P1 810013 NW - 1200 X Table II B (continuation) Pressure application Number of empty jacket tubes (2) Filling type wet clearance P through piston Passes paste in to "fill" the A by air (1) the plate plate, g 4B without 2 - A 306 5A without rapid filling, with the exception of A - of 1 tube 5B without 2 all Tubes filled - 362 810201 6A - 10 tubes empty A -6B - little change - -6C - 3 - - -810202 7A - B 168 7B - - 266 7C - - 272 7D - 4 - 277 810203 8A - B 203 8B - 2 - 288 T a b e l l e II C Bei- N = negative tube time to for air inlet play through the plate P1 = positive 1 small filling of the trodden areas, X straight end P2 = positive 2 type plate under slurry volume, Y diffuser end solids Mud gravity, ml O (3) liquid code number sec 810204 9A 0.75 / 1 P1 810013 NW 3 - 5 1200 X O 9B 0.75 / 1 P1 810013 NW - 450 X O 810205 10A 0.5 / 1 P1 810015 NW 5 500 without 10B 0.5 / 1 P1 - 200 without 10C 0.5 / 1 P1 600 without 810206 11 0.5 / 1 P1 810015 NW 5 550 X O 810207 12A 0.5 / 1 P1 810015 NW 5 1200 X O 12B 0.5 / 1 P1 810015 NW - 1200 X O Table II C (continued) When printing number of blank Jacketed tube (2) Filling type wet play P through piston pass the paste in A through Air (1) to "fill" the plate Plate, g 810204 9A - all tubes filled B 366 9B A 2 - - -810205 10A - 9 tubes filled B 226 10B A 3 additional tubes filled 276 10C A 6, 12, 13, 14 263 (4a) 810206 11 - - 3, 5, 6, 7, 8, 9, 10, 15 empty B 173 810207 12A - - B 12B - 2 6, 10, 11, 12, 15, empty - 228 After these attempts a severe clogging of the manifold with large graphite particles occurred, despite flushing the compressed air leg 208 and manifold. That's why a Part of the largest particles screened out.

T a b e l l e II D Bei- N = Negative tube time until through the Plate air introduction play P1 = positive 1 small filling of the trampled volume, X straight End P2 = positive 2 type plate under sludge volume, Y diffuser end solids sludge Gravity, ml O (3) liquid code number sec 810208 13 0.5 / 1 P2 810017 NW 5 1200 without 810209 14A 0.5 / 1 P2 810017 NW 5 1200 X O 14B 0.5 / 1 P2 810017 NW 5 700 X O 14C 0.5 / 1 P2 810017 NW 5 1500 X O 810210 15 0.5 / 1 P2 810017 NW 3 1200 Y O 810106 16A 0.56 / 1 N 810004 NW 2 400 Y O 16B 0.56 / 1 N 810004 NW - 100 Y O 16C 0.56 / 1 N 810004 NW - 200 Y O 810107 17 0.46 / 1 N 810005 NW 3 1500 Y O 810108 18 0.46 / 1 N 810005 NW 2 - 5 500 Y Table II D (continued) When applying pressure number the empty jacket tube (2) filling type wet game P through piston passes paste A by air (1) to "fill" in the the plate plate, g 810208 13 without 1 11, 13 empty B 348 810209 14A without - 5 tubes empty B -14B without - 3 tubes empty B 313 14C without 3 6, 8, 9 empty - -810 210 15 without 1 all tubes filled B 355 810 106 16A - 13, 14, 15 empty B -16B A1 - - -16C A1 3 - 283 810107 17 - 1 14, 15 empty B 311 810108 18 - 1 all tubes filled, B 359 slight pellet formation at 1, 2 and 3 (2a) T a b e l l e II E Bei- N = negative tube time until air is introduced through the plate game P1 = positive 1 filling of the stepped sum, X straight end P2 = positive 2 type plate under sludge volume, Y diffuser end solids sludge gravity, ml O (3) liquid code number sec 810109 19A 0.46 / 1 N 810005 NW 2 - 5 1500 Y O 5A 0.56 / 1 N 810004 NW - 600 without 19B 0.46 / 1 N 810005 NW - 1500 Y O 810110 20 0.25 / 1 N 810006 NW 5 1500 Y O 810111 21 0.25 / 1 N 810006 NW 5 1500+ Y O 1500 810112 22A 0.75 / 1 N 810007 NW 5 1500 Y O 22B 0.75 / 1 N 810007 NW - 1500 Y O 810113 23 0.75 / 1 N 810007 NW 5 1500 Y O Table II E (continued) When applying pressure Number of empty jacket tubes (2) Filling type wet clearance P through piston passages Paste A by air (1) for "filling" in the plate plate, g 810109 19A - 8, 13, 14, 15 B 270 19B - 2 8 (1/2 full), 13, 15, empty - 298 810 110 20 A2 1 15 empty B 309 810111 21 A2 1 all filled B 336 810112 22A - tube blocked B 236 22B A2 2 8, 9, 14, 15 empty B 278 810 113 23 A2 1 4, 11, 13 empty, 12 (1/2 full) B 258 14 (1/2 full) T a b e l l e III Case Active Solids Characteristic Stratification A - D middle deflection material liquid figure top middle bottom valuation, % D C B (bottom) A 18 negative 0.46 / 1 810 108 161 164 169 175 14 167 + 5-4 21 negative 0.25 / 1 810111 156 158 162 165 9 160 + 3-2.5 22B Negative 0.75 / 1 810112 163 156 162 161 -2 160 + 2-2.5 13 Positive 2 0.5 / 1 810208 168 164 165 158 -10 164 + 2.5-4 10C Positive 1 0.5 / 1 810205 173 154 153 133 -40 153 + 13-13 A comparison of the Examples 10C and 13 in Table III show the vastly improved uniformity the filling when using positive active material (all particles <500 The comparison of Examples 13 and 14 with Example 15 shows the superiority with regard to the filling weight that is obtained when using the modified air diffuser 216 in the mailing list.

B e i 5 p i e 1 e 24 to 59 Examples of specific plate-making processes are given using the apparatus shown in Figures 15 and 16.

In some of these examples the same plates are used, as described above for Examples 1 to 23, that is, they are non-woven Polyester sheaths with 15 jacket pipes each, which are connected to one another, and cast lead pin assemblies are used. These are in the following Tables IV A to IV C are denoted by the symbol "If".

In other examples, the same molded lead pin arrangements, however, different wrapping arrangements, consisting of 15 individual ones, from one another separate jacket pipes used. Each jacket tube has a perforated outer Polyvinyl chloride wrap and an inner woven glass fiber tube. These will denoted by the symbol "PG" in Tables IV A to IV C below.

Each of these jacket pipes has an outer, continuous PVC sheath 2.9 cm in circumference, seven holes are arranged along this circumference, and in 2.9 cm long along the axis of the envelope are also seven Holes.

The holes are thus arranged on square centers, however offset from each other by 45 °, so that lines of holes around the circumference 'of the jacket pipe around at an angle of 45 ° precess. Each hole is 2mm Diameter, and the inner diameter of the polyvinyl chloride envelope is 9 mm. The thickness of the envelope is about 0.2 mm.

In the jacket pipe there is a cohesive, seamless one Fiberglass tubing made from staple threads that have a flat cross-section and about 0.5 mm wide and in turn made of staple glass fibers 1 to 2 cm in length are completed. The threads are at about 45 ° diagonally along the length of the jacket pipe woven, where there are 60 individual threads, each of which is made up of two thinner threads is twisted together with a small twist of about 5 twists per cm are. The individual threads themselves have an extension of about 0.3 mm and are very flat; the thickness is only about 0.05 mm. The inner volume of the enveloped Plates marked "PG", that is, for filling with the active one Material available volume is 270 ml.

Comments on Tables IV A to IV C (t) Example (2) Solids / Liquid (3) Sludge code number (4) Casing pipe type (5) Time until the start of the pressure increase, t1 in sec (6) pressure increase (overpressure) until switch-off, in kg / cm2 (7) total time until shutdown, t2 in sec (8) duration of pressure application, t2 - t1 in sec (9) compressed air introduction (10) Empty jacket pipes; the jacket pipes are, starting from the end of the flag, with numbers Numbered from 1 to 15 (11) Type of filling (A = injection filling, B = filtration filling) (12) Wet paste in the plate, in g (13) Dried paste in the plate, in g (14) Sludge tank air stirrer 255 (Figure 15), liters of air / min (15) Compressed air 258 (Figure 15), liters / min T a b e l l e IV A (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) 411 100 0.21 / 1 41101 NW 12 1.40 24 12 yes none B 310 137 56 30 24 NH2 411101 0.20 / 1 "" 22 1.40 42 20 yes "" 309 141 "20 25 411102 0.40 / 1 41102 "6 1.40 7.5 1.5 no 10" 317 148 72 -26 12 (1/4) 411103 0.39 / 1 "" 5 1.40 6.5 1.5 yes none "319 185" 40 27 411104 0.37 / 1 "" 4 2.17 8.5 4.5 no "" 293 141 "30 28 411105 0.36 / 1" "4 2.10 10 6 yes 13" 280 148 "30 29 411110 0.37 / 1 41110 "4 1.40 8 4" none B 342 207 "" 30 NM3 411111 0.27 / 1 "" 4 2.10 11 7 "" BA 280 125 "" 31 411112 0.26 / 1 "" 8 1.40 12 4 "" "269 122" "32 411113 0.14 / 1 "" 14 1.40 25 11 "" B 320 150 "" 33 411 114 0.12 / 1 "" 26 0.70 46 20 " "B 305 131" "34 411200 0.25 / 1 41201" 9 0.70 23 14 "" "419 225" "35 NO1 411201 0.21 / 1 "" 18 0 - - "" "375 180" "36 411 202 0.20 / 1" "14 0.84 24 10" "" 420 217 "" 37 T a b e l l e IV B (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) 411203 0.67 / 1 41202 NW 8 1.40 12 4 yes none B 462 278 72 30 38 NO1 411204 0.45 / 1 "" 10 0.98 21 11 "" B 435 258 "" 39 411206 0.42 / 1 41203 "6 0.70 18 12" "BA 448 300" "40 411207 0.31 / 1" "4 1.40 7 3" "A 382 217 "" 41 411208 0.50 / 1 41208 PG 4 0.28 37 33 "2 (3/4) B 550 379" "42 411209 0.45 / 1 "" 45 - - - "none AB 442 257" "43 411210 0.44 / 1 41210" 29 - - - "" A 382 177 "" 44 411211 0.41 / 1 41211 "10 0.07 16 6" "A 426 243" 45 45 411212 0.39 / 1 "" 10 0.42 22 12 "" A 417 217 "55 46 411213 0.35 / 1" NW 10 0.98 28 12 "" A 337 201 "" 47 411214 0.34 / 1 "" 4 2.10 22 18 "" A 333 198 "" 48 411215 0.33 / 1 "" 10 0.7 52 42 "" A 320 191 "" 49 511000 0.25 / 1 51000 NW 12 1.40 26 14 "4 B 342 200" "50 511PGS 511001 0.23 / 1" PG 24 - - - "all B 200 97" "51 empty T a b e l l e IV C (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) 511002 0.51 / 1 NW 8 - 16 8 yes none B 388 245 72 55 52 511003 0.48 / 1 PG 14 - - - "4" 412 239 "15 53 511004 0.46 / 1" 16 - - - "7" 385 224 "" 54 511005 0.40 / 1 51005 "10 1.40 20 10" none "375 188" "55 NH2 511006 0.36 / 1" "10 0.70 18 8 no "" 395 186 "none 56 511007 0.35 / 1" "10 1.40 20 10 yes" "401 193" 30 57 511008 0.35 / 1 "NW 8 1.40 13 5" "" 345 170 "30 58 511009 0.34 / 1" PG 10 1.05 25 15 "" "399 192" 30 59 A pump setting of 110, accordingly 5 liters of Wa'erAnin is used in all examples. In the following tables V A and V B are the details regarding viscosity, settling properties and the half-life of the sludge used.

Rotary vane viscometer torque values are used in the examples (and in the description) for characterizing easily pourable sludges with low viscosity. The values given in Tables I, V A and V B are read values and not the torque values that characterize the preferred slurries are used. For converting the torque values read off Table I on the torque values used for definition is the background value of 0.28 g. Subtract m (0.002 lbs. ft) from the measured values and add the Tables V A and V B is the background value of 0.14 g. m to deduct. In particular Example len, for example in Examples 41101 and 41201 of Table V A, 41210, 51000 and 51005 of Table V B, as well as the example 810017 of Table I. the sludge has the same viscosity value as the background value. So that is measured or read torque value is not greater than the background value at the measurement carried out, and these slurries thus meet the preferred viscosity properties, that means they have a torque value of less than 0.83 m. g (0.006 lb.ft) at 20 Orc The compositions and sieve analyzes of the used in the slurries Materials are given below.

NH2 is a negative active material that, related by weight, 78 percent cadmium hydroxide, Cd (OH) 2, 5 percent cadmium, 15 percent Contains iron oxide, Fe203, and 2 7D graphite.

NH3 represents the NH2 material after sieving to remove particles with over 40 mesh.

N01 consists of 100 percent by weight of cadmium oxide.

511 PGS is a material that is made up of the above Positive 1 material is produced as follows: The positive material is sieved, 5950 e pass through a 40 mesh screen (BS 410 Normal). The material that this sieve does not pass, it is ground in a ball mill for 16 hours. This ground material is then subjected to sieving, whereupon 450 g of the material, that passes through a 40 mesh sieve with the 5950 g that passed through the first sieve are going to be united.

The sieve analysis of the individual materials is given in Table VI.

T a b e l l e V A Sludge- used Active solids measured Rotational viscosity settling half-life characteristic in material liquid meter torque values *) of the sample, the suspension number example shear-twist-peak% sion, sec speed. moment Rpm g. m 41 101 24 NH2 0.21 / 1 6 0.14 no 38 7 24 0.14 42 0.14 41 102 26 0.40 / 1 6 0.42 no 93 -24 0.14 42 0.14 41 110 30 NH3 0.37 / 1 6 0.28 no 93 -24 0.14 42 0.14 41201 35 NO1 0.25 / 1 6 0.14 no 74 525 24 0.14 42 0.14 41202 38 NO1 0.5 / 1 6 0.42 no 95 -24 0.42 42 0.42 *) The background torque value is 0.14 g. m (0.001 1bs. ft T a b e l l e V B sludge- uses active solids measured rotational viscosity settling half-life characteristic in material liquid meter torque values *) of the sample, the suspend figure example shear-twist peak % sion, sec speed torque rpm g. m 41203 NO1 0.67 / 1 6 0.14 no 100 -24 0.14 42 0.14 41208 NO1 0.5 / 1 6 0.42 no 91 -24 0.14 42 0.14 41 210 NO1 0.5 / 1 6 0.28 no 88 -24 0.14 42 0.14 41 211 6 0.14 no 96 -24 0.14 42 0.14 51000 511PGS 0.25 / 1 6 0.42 no 20 41 24 0.42 42 0.42 51005 NH2 0.4 / 1 6 0.14 no 97 -24 0.14 42 0.28 T a b e 1 1 e VI Active material N01 NH2 NH3 511 PGS mesh BS 410 Normal> 16> ] 1000 O O O O <16 <1000 100 100 100 100 <22 <699 100 95 100 100 <30 <500 100 81 100 100 c 60 <250 98 60 90 94 <100 <150 34 41 66 77 <150 10 <105 28 33 64 67 <350 <45 7 6 9 20 The examinations to determine the electrical suitability of test cells, their manufacture with certain Plates of Examples 24 are described below.

Plates made with negative active NH2 or NH3 material were, namely the plates of Examples 26, 27, 30 and 33, are in the test cell Soaked for 16 hours in potassium hydroxide (KOH) with a density of 1.20 at 20 0C.

The capacity cber. becomes from the dry weight of the active material determined in the cell. The plates are used for 14 to 16 hours at a current in amps of Cber./10 so that the cell has about 150 percent of the capacity Cber. fed will.

The cell consists of two conventional standard plates, the negative plate to be examined hangs between the standard plates. The distance to the standard plates is 3 to 5 mm; every gap becomes a piece of one alkali-resistant polymer mesh with a thickness of about 0.5 mm inserted. The openings in the network have dimensions of about 2 to 3 mm. Examination of the cells takes place by discharging at a current in amperes of Cber./5 at 20 C.

The results of two different discharge conditions are compiled in Tables VII A and VII B below.

Certain panels made with the active cadinium oxide material N01 (Examples 38 and 47) are soaked in KOH, and as above described, loaded. Other panels (Examples 48 and 49) will last 16 hours Soaked 20 0C in aqueous nickel sulfate (20 g / liter), then rinsed in water and finally drained for 5 minutes. Then the plates are in KOH (1.20 g / ml) immersed and then loaded as described above.

T abe 1 1 e VII A Conserved capacity up to 1 volt Plat- Bei- Cber t Cycle 1 Cycle 3 Cycle 8 Active Mate Characteristic Ah from von; a from rial digit Ah upper. Ah Cber. Ah Cber. 411 102 26 28 0.9 3 5.2 19 15.7 56 NH2 411 103 27 35 1.2 3.5 4.9 14 14.4 41 NH2 41 110 30 39 1.8 4.6 8.0 20 19.2 49 NH3 411 113 33 28 1.2 4.3 6.9 25 16.6 59 NH3 411 203 38 73 28.5 39 23.5 32 40.7 56 Nol 411 213 47 53 24.6 46 18.5 35 17.4 33 NO1 411214 48 52 18 35 27.3 52 23.7 46 N01 411215 49 50 18.7 37 29.2 58 23 46 N01 T abe 1 1 e VII B Maintained capacity up to 0 volts 411 102 26 28 4.6 16 13.4 48 30 107 NH2 411 103 27 35 4.1 12 11.2 32 27.8 30 re2 411 110 30 39 3.8 9 , 7 14.2 36 28.9 74 NH3 411 113 33 28 3.2 11 12.2 44 25.3 90 NH3 411 203 38 73 41.5 57 40.5 55 47.4 65 NO1 411 213 47 53 33.8 68 28.8 54 30.2 57 NO1 411214 43 52 26 50 37.6 72 35.2 68 N01 411215 49 50 26 52 36.2 73 34.5 69 NO1 As already mentioned, other electrochemically active substances besides alkaline, active nickel-cadmium material suitable for the method of the invention.

Of course, in such alternative embodiments components used must be compatible with one another. If, for example, alkaline, negative active material are used, the souls are preferably composed the end a metal that has sufficient chemical corrosion resistance in an alkaline environment. Examples of this are steel discharge pins with round or strip-shaped cross-section, which can be nickel-plated. Instead of the polyester casing pipes can, for example, casing pipes made of polyamides or nylon be used. Preferred examples of the alkaline electrochemically active material are nickel hydroxide for the positive plate and cadmium hydroxide for the negative Plate. These typically contain a proportion of electrically conductive material, For example, sufficient amounts of graphite to achieve an appropriate conductivity guarantee.

Preferably about 5 to 15 weight percent graphite is used. Steel can be used as an electrically conductive element and in a suitable porous form to ensure it the filtration filling. Another example of alkaline electrochemical active material is iron oxide for the negative active material.

The nickel hydroxide can also contain nickel particles or flakes Form to improve conductivity included.

The iron oxide can also be used to improve the conductive material Conductivity included.

Aqueous potassium hydroxide is typically used as the electrolyte, which may contain a small amount of lithium hydroxide.

According to the invention, the use of chemically inert casings is possible. However, this excludes the filling of the casing pipes with metallic or other shapes of the active material and its chemical or electrolytic conversion into the electrochemically active form within the envelope is not excluded. The invention includes thus also such embodiments. Accordingly, the term "active mass" includes also such material that is inside the porous envelope, either before or after the assembly to plate sets, converted into the electrochemically active form can be.

An example of this aspect of the invention is use of cadmium oxide, CdO, instead of cadmium hydroxide, Cd (OH) 2, in the negative sludge. CdO is more dense or specifically heavier than Cd (OH) 2, and thus a larger Weight can be introduced into a given casing pipe volume. The CdO can be transferred are converted into the active form, Cd (OH) 2, by immersion in nickel nitrate or nickel sulfate, whereby the brown CdO powder is converted into a greyish white sludge. It is a still incompletely explained reaction in which may be hydrolysis.

There are numerous other electrochemically active combinations, which are suitable for use in accumulators or batteries.

The procedure is so far in connection with secondary systems or rechargeable systems. However, it is equally on primary Battery systems applicable where the active materials or hosts thereof in one porous envelope and enclosed in the envelope as a liquid, suspended, preferably aqueous, sludge can be introduced.

The liquid used as a suspending agent for the sludge In the simplest case, it is water (or

aqueous solutions) for several reasons, such as cost, safety and inertness, is clearly preferred. However, if the use of an aqueous Would cause problems for the carrier, this could be through another liquid Carrier can be replaced, which is suitable for the active material used.

Examples of other battery systems for which the method of the invention Can be used are summarized in the following Table VIII.

The active materials listed below become particulate with suitable particle sizes used to make a filtration fill with the used to achieve porous envelope. T a b e l l e VIII Battery positive negative electrolyte primary remarks system electrode electrode or secondary A zinc carbon ammonium chloride primary or potassium hydroxide B zinc carbon, "" catalyzed with precious metals or base metals such as copper C zinc manganese oxide / carbon ammonium chloride "Mixtures with a carbon collector lamella D zinc" Potassium hydroxide secondary E zinc Graphite, cataly- "Primary through the negated with precious metal electrode or basic material, air is dumped like copper sends, with ionization taking place.

Table VIII (continued) Battery positive negative electrolyte Primary remarks system electrode electrode or F iron like E like E like E like E G Cadmium "" "" H Magnesium Manganese dioxide / carbon-potassium hydroxide "Mixtures with a potassium chromate carbon collector ala potassium chlorate melle I mercury cadmium oxide (CdO) aqueous potassium- "ber- (I) - hydroxide J nickel graphite, cataly- potassium hydroxide Secondary The electrodes are set with precious metals - they are metal or base in one solid metal, such as copper sealed container that is saturated with hydrogen gas is. The electrodes consume hydrogen during discharge and release hydrogen free while charging.

Claims (31)

P a t e n t a n s p r ü c h e Process for the production of armor plates, especially for accumulators, by introducing an active, liquid-glass-containing mass into the porous envelope of the plate when the envelope is placed on the conductive element of the plate is that it is not possible to use an alkaline substance as the active substance active mass with such a large liquid content used that the active material is filtered out through the porous envelope, while liquid is filtered out through the walls the porous envelope passes through. 2. Process for the production of armor plates, especially for accumulators, by introducing an active material into the porous envelope of the plate, if the Enclosure is arranged on the electrically conductive element of the plate, characterized in that that an alkaline active mass is used as the active mass and this into the Feeding coating as an aqueous sludge when the coating is in substantially vertical plane so that the solids reach the bottom of the casing can settle down under gravity, the aqueous sludge being a weight ratio of active material to water in the range 0.1: 1 to 0.75: 1, the The material of the envelope is selected so that it filters out active material, while liquids are permeated, removing the solids at least partially be held within the envelope and the liquid at least partially able to escape through the walls of the casing, and the feed of the sludge continues into the envelope until the envelope is filled with active material is whereupon the pressure in the feeder to the envelope is reduced to a value of over 0.35 kg / cm2, but not more than 7 kg / cm2, and then the pressure is released brings about. 3. The method according to at least one of claims 1 and 2, characterized characterized in that an arrangement of casing pipes is used as the casing, side by side on one conductive element, each one conductive element in each jacket tube, are arranged. 4. The method according to claim 3, characterized in that one is a Ratio of the volume of sludge that is fed into the casing pipes to the total internal free volume of the casing pipes used in the plate of at least 2: 1. 5. The method according to claim 4, characterized in that one is a Ratio of 3: 1 to 15: 1 used. 6. The method according to at least one of claims 1 to 5, characterized characterized by making a slurry with a rotary vane viscometer torque value less than 0.83 m. g used at 20 0C. 7. The method according to at least one of claims 1 to 6, characterized characterized in that after filling the envelope, the counter pressure in the sludge feed for coating can be increased to a value in the range of 0.35 kg / cm². 8. The method according to at least one of claims 1 to 7, characterized characterized in that one has a wrapping material with a nitrogen permeability used in the range of 0.5 to 20 liters / cm2 / min. 9. The method according to claim 8, characterized in that one is a Wrapping material with a nitrogen permeability in the range of 3 to 10 liters / cm² / min used. 10. The method according to at least one of claims 1 to 9, characterized characterized by using a sludge containing cadmium hydroxide active material with 70 to 90 percent cadmium hydroxide, up to 10 percent cadmium, up to 5 percent Contains graphite and up to 15 percent iron oxide, the ratio of solids to liquids in the range of 0.25: 1 to 0.75: 1. 11. The method according to claim 10, characterized in that the dipped the filled tube plates into a base before loading. 12. The method according to at least one of claims 1 to 9, characterized characterized in that one uses an alkaline active material which, either before or after the assembly to the cell, in the porous envelope in an electrochemical active form can be converted. 13. The method according to claim 12, characterized in that one is a alkaline active material used, the cadmium oxide and optionally up to Contains 10 percent graphite and possibly up to 20 percent iron oxide, and the Plate after filling a treatment to convert the oxide to the hydroxide subject. 14. The method according to claim 13, characterized in that the The plate is immersed in an aqueous nickel salt solution for treatment. 15. The method according to at least one of claims 13 and 14, characterized characterized in that one has a ratio of solids in the aqueous mass Liquid in the range of 0.7: 1 to 0.2: 1 is used. 16. The method according to at least one of claims 1 to 9, characterized characterized in that one uses an alkaline active material, the nickel hydroxide and contains up to 20 weight percent graphite, the ratio of solids to liquid in the sludge is in the range of 1.5: 1 to 0.2: 1. 17. The method according to at least one of claims 1 to 16, characterized characterized in that one uses a sludge in which all solid particles have a size of less than 1000 P. 18. The method according to at least one of claims 1 to 17, characterized characterized in that a sludge is used, the solid particles of which are 100 Weight percent have a size of less than 500> i, with no more than 25 Weight percent are below 45 u. 19. The method according to at least one of claims 1 to 18, characterized characterized in that a stream of air or gas, preferably compressed air, into the Sludge, immediately before its entry into the porous envelope, introduces to any tendency for the solids to separate out of the sludge prior to entry of the sludge in the porous envelope. 20. The method according to claim 19, characterized in that the Air or gas flow is supplied at a rate of 2 to 55 liters / min. 21. Alkaline battery electrode, characterized by a porous one Encapsulation with particulate active material contained therein which is electrochemically is active or under alkaline conditions in an electrochemically active form can be converted, the porous envelope being a bed of active material from an aqueous slurry of the active material containing 0.5 parts of the active material contains water per part, able to filter out. 22. Electrode according to claim 21, characterized by one or more inner conductive elements with an outer current conductor for the plate are connected. 23. Electrode according to at least one of claims 21 and 22, characterized by one or more stromleitentle elements that are externally related to the porous Enclosure are present, the porous envelope being conductive. 24. Electrode according to at least one of claims 21 to 23, characterized characterized in that the porous envelope consists of a metallized, non-metallic material. 25. Electrode according to claim 24, characterized in that the metallized, non-metallic material a needled two-component material made of alkali-resistant Fibers is used for electrical conduction 0.01 to 0.20 g of an alkali-resistant 2 metal per cm. 26. Electrode according to at least one of claims 21 to 25, characterized characterized in that the porous envelope consists of an outer, strength-imparting, coarse-porous container and an inner, finely-permeable filtration layer. 27. Electrode according to claim 26, characterized in that the outer Container is metallic, so that it contains the active material in a tightly compressed form can accommodate. 28. Electrode according to at least one of claims 26 and 27, characterized by an inner electrically conductive element, with the ends of the outer, strength-imparting element Container are closed by alkali-resistant polymer stoppers through which the ends of the inner conductive element extend, the outer ends of the electrically conducting element (or devices) engage in these ends, and the Hold the plugs in place in the ends of the container. 29. Electrode according to at least one of claims 21 to 28 before the electrolytic formation, the active material being particulate cadmium oxide represents, optionally up to 10 percent graphite and optionally up to Contains 20 percent iron oxide. 30. Device for filling armor plates, especially for accumulators, characterized by at least one Füllstac tion with facilities for holding the cladding of a plate that rests on the conductive element in essentially is arranged in the vertical plane, a filling distributor device for To ## aspeisung of sludge in the envelope of a plate which is arranged in the holder, a sludge storage tank with Re # facilities for receiving a supply of active M Mater sludge, dispensing devices for dispensing the sludge from the storage tank to the distribution device of a selected filling station, as well as compressed air devices for introducing an air or gas flow into the distribution device. 31. The device according to claim 30, characterized in that the Compressed air device contains a perforated pipe, #laze up to the vicinity of the Center of the distribution device extends. L e r s e i t e