GB1602383A - Lead acid cells and batteries - Google Patents

Description

(54) LEAD ACID CELLS AND BATTERIES (71) We, CHLORIDE GROUP LIMITED, a Company registered under the laws of England, of 52 Grosvenor Gardens, London SW1W, OAU, England, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described, in and by the following statement: The present invention relates to so called sealed lead acid electrochemical cells, and batteries made up from such cells.

So called sealed lead acid cells are supplied with their electrolyte content during manufacture and do not require to have electrolyte or water added during their lifetimes; such cells are usually referred to as sealed cells but in fact are usually provided with venting means so that in the event of excessive pressure build up occurring during certain phases of use, e.g., on overcharge, the excess gas can be vented to atmosphere and rupturing of the cell avoided.

Various proposals have been made for cells of this type but none are entirely free from problems.

The invention is not dependent on any particular cell geometry and is applicable both to wound cells and to prismatic cells. Wound cells have a single negative plate in the form of a long strip separated, by a long strip of porous electrically insulating separator material, from a single positive plate also in the form of a long strip. These are wound about an axis transverse to the length of the strip to form a compact interleaved electrode assembly.

Prismatic cells are formed from multiple numbers of separate positive and negative plates of square or rectangular forms separated by one or more sheets of separator material.

Thus according to the broadest aspect of the present invention a sealed acid cell as defined herein is characterised in that it has electrodes comprising metallic supports which minimize the evolution of hydrogen and resist deformation under their own weight, the supports for the electrodes being in the form of a mesh or grid affording an integral current collecting strip or bar along at least one edge which will be the top or bottom edge or the structure when assembled in a cell and the supports for the electrodes being made of a lead-calcium-tin alloy containing 0.04% to 0.1% by weight calcium and from above 0.5% to 1.0% tin, and which are separated by at least one layer of separator material, the support of the positive electrode or electrodes having positive active material deposited thereon, and the supports of the negative electrodes or electrodes having negative active material deposited thereon, and in which the capacity of the negative electrodes is arranged to be at least as great as the capacity of the positive electrodes, the thickness of each electrode is less than 3 mm, the thickness of the separator is in the range of 10% to 200% of thickness of the electrodes and the volume, E, of the electrolyte in the cell in relation to the sum of the pore volume of the separators, X, and the pore volume of the positive and negative active materials, Y, is not greater than 2X + Y.

The metal grid is one which does not encourage production of hydrogen overpotential and thus minimises evolution of hydrogen. Such materials include 99.99% pure lead but this is difficult to handle because it is not self-supporting to any degree and the current conductor structure is thus liable to distortion during assembly. Moreover, such metals are highly susceptible to growth and creep under stress in service. Structures are therefore used which resist deformation under their own weight whilst retaining the desirable characteristics of minimising evolution of hydrogen. The alloys used contain 0.04 to 0.1% calcium e.g., 0.06 to 0.08%, and from above 0.5 to 1.0% tin e.g. 0.6 to 0.9%; the alloy may also include aluminium, sodium and magnesium in amounts of up to at least 0.1% e.g., up to 0.2, 0.3, 0.4 or 0.5% by weight either individually or in combination. A preferred specific alloy contains 0.7% tin and 0.07% calcium.

The metallic supports may be cast strips or grids or wrought metal structures such as slit and expanded strips and sheets through these latter materials are liable to loss of shape during handling and pasting and are also susceptible to corrosion problems.

We thus prefer to use wrought structures which are non-distortable in thickness, e.g.

perforated or stamped or rolled or slit sheets having apertures therein defining a mesh or grid structure.

The metallic supports are provided with a current collecting strip or bar along at least one edge which will be the top or bottom edge of the structure when assembled in a ell. This has the advantage of reducing corrosion because high current density concentrations, which may occur when individual spaced apart current collecting lugs are used, are avoided.

This current collecting strip may be integral with the structure or formed separately and attached thereto. Its cross-sectional area is desirably at least twice that of the narrowest elements of the structure and desirably at least 3,4,5 or 10 times the cross-sectional area of the thickest element of the structure apart from the said current collecting strip.

The current collecting strip for the plate or plates of one polarity may be connected by a yoke or link to a terminal for that polarity by conventional means but is preferably connected by a novel slotted bar arrangement which fits over the current conducting strip or one polarity and is crimped or welded thereto. The bar preferably has an integral tab which can be led out of the cell to form the terminal or to be connected, e.g., by spot welding, to the tab of an adjacent cell in a battery.

It is preferred to enclose one of the electrodes or electrode polarities in an envelope of separator material which may be open or closed at the ends in the case of a wound assembly or at the sides in a prismatic assembly.

Preferably the positive electrode is enclosed in the envelope with the closed end of the envelope at what will be the bottom end of the positive in use; the positive is thus connected to the terminal yoke at its upper edge.

The metallic support structures may be pasted by conventional means with conventional positive and negative paste compositions.

The active materials are preferably made as porous as possible, preferably the porosity (void volume) of the positive plate should be at least 50%, preferably in the range 50% to 55% or 65% as measured by mercury intrusion penetrometry.

However in a preferred form of the invention the positive active material paste composition contains at least 23, 25 or 28 or 52 to 57 parts by weight of liquids per 100 parts by weight of active material (calculated as PbO2) and at least 0.01, preferably 0.05 and desirably at least 0.1 to 1.0, preferably 0.3 to 0.7, e.g. 0.4 to 0.6, parts by weight of silica calculated as SiO2 per 100 parts by weight of active material (calculated as PbO2). These compositions are thixotropic and this facilitates pasting as well as resulting in a material of high porosity.

The negative active material may contain conventional lignite organic negative active material expanders and conventional inorganic negative active material expanders, e.g., barium sulphate. However, we prefer to use lignin derived negative active materials instead of lignite materials especially with the preferred positive active material described above.

The preferred materials are lignosulphonate materials made by digestion of wood pulp with aqueous alkalis and alkaline bisulphites followed by partial oxidation to lower the organically combined sulphur content of the material. Materials of this type are sold under the trade mark VANISPERSE and one suitable material, sold as VANISPERSE CB, is described in detail below.

The separator is selected to have a good moisture retention, a good rate of wicking, i.e. it picks up and permits liquids to wick rapidly through it by capillary action and a good gas (especially 02) permeability so as to retain electrolyte within its pores readily and also to permit rapid passage of gas through it even when containing electrolyte.

The separator preferably has a void volume in excess of 40%, e.g., at least 50% or 60% or 70 or 80 or 95%. Non-woven fibrous mats may be used as separators especially glass fibre mats preferably having a thickness in the range 50% to 150% of the thickness of the positive or negative plate, e.g., in the range 0.5 to 3.0 mm or more broadly 10% to 200% of the thickness of the positive or negative plate.

The separator may be formed of repeating spaced macro areas having varying moisture absorption and retention characteristics. These areas may be dots, patches or strips, either horizontal or preferably vertical of reduced moisture absorption, which will have increased gas permeability. In one such arrangement, the areas may comprise 1% or 5% to 90% of the area of the separator and preferably 10% to 40% and are desirably distributed evenly over the area of the separator. They may be formed by making the separator of materials of intrinsically varying moisure absorption characteristics, e.g., hydrophobic materials, e.g., silicones or polymer dispersions e.g., polytetrafluorethylene emulsions, at the regions where reduced moisture absorption is desired.

In another alternative the material is relatively porous and is compressed in certain regions, preferably as vertical channels, to as to reduce its gas permeability but increase its moisture absorption and wicking rate.

In so called sealed cells, gases generated during operation, e.g., hydrogen and oxygen, can either be recombined with each other, e.g., at catalytic locations, or more preferably, the cell is arranged so that only oxygen is liable to be generated, e.g., on overcharge, and the cell is arranged so that this oxygen under all but exceptional circumstances can react with negative active material thus preventing excessive pressure build-up.

Gases generated at the positive permeate through the separator to the negative to recombine therewith directly.

In order to ensure that the system will be such that the positive is under all conditions charged before the negative is charged and thus that only oxygen is liable to be evolved on overcharge the negative capacity is arranged to be at least as great as that of the positive and desirably greater, preferably at least 1%, 4, 10 or 20% greater in ampere hours at the 5,10 or 20 hour rates of discharge.

Equally, the mass of negative active material may be arranged to be at least equal to and desirably at least 1%, 5,10 or 20% greater than the mass of positive active material.

The electrode thicknesses are less than 3mm., particularly 0.5 to 2.0 or 1.5 or 1.0 mm.

The ratio of electrolyte volume to the sum of the pore volume of the separators and the pore volume of the positive and negative active materials is preferably at least 1:1 in the cell, preferably 1:1 up to 1.25:1.

Wound electrode assemblies have the advantage of a high energy per unit volume as individual cells. However; when these cells are combined into batteries, a waste of space occurs with cylindrical cells. We thus prefer to wind our assemblies around square or rectangular formers which may be hollow, solid or porous, hollow or porous formers being preferred; the porous formers may be mesh or grid shaped or made of sintered crumbs, preferably 1 to 3 to 5 mm. across which produce a coarsely porous material having a low water absorption. The former may have an arcuate slot formed in it to receive and clamp the inner end of the electrode/separator/electrode assembly which is preferably wound with the negative on the outside.

The cells may be enclosed in a plastic container, preferably of polypropylene or polyethylene, which is acid resistant but not necessarily burstproof. Pressure containment may be provided by packing the cells into a rigid battery box either of metal or reinforced plastics preferably reinforced by external ribs. Rectangular or square cells have the advantage of needing little or no extra support and alignment of the cells in the battery is simple. The cells may be provided with individual venting valves, preferably of the so-called Bunsen type, or preferably are merely provided with an upstanding reinforced collar in the lid sealed with a thin perforatable thickness of polymer. (The cell lids may be an integral moulding).

This enables the cells to be stored fully sealed after manufacture until assembly into a battery, e.g., for automotive use.

This thin seal can then be perforated immediately before assembly of the cells into a battery, The upstanding collar on the lid then acts as a valve seating for a resilient, preferably, elastomeric, valve strip, which may be continuous, located in the manifold and arranged to normally seal the outlet from each cell.

The cells are desirably filled with electrolyte by being flooded therewith, electrolytically charged, evacuated to draw off gasses from the pores of the separator and the active material and replace them with electrolyte and then excess electrolyte is allowed to drain off under gravity. The volume of electrolyte is thus at least equal to the pore volume of the separator and active material combined. In the preferred arrangement in which an electrolyte reservoir is provided the volume of electrolyte present in the cell is about 5 to 30% e.g., 10 to 20% greater than the pore volume of the active material and the separator.

The modular possibilities of these cells would permit one to make up batteries of varying performance by series/parallel assemblies of a standard cell, e.g., a 2 volt 5 amp hour cell could be used to make a 12 volt 5 amp hour battery by connecting six cells in series, a 2 volt 10 amp hour battery by connecting two cells in parallel and a 12 volt 60 amp hour battery by connecting in series 6 pairs of cells connected in parallel.

When a bottom current collecting link is being used there may be a dead space at the bottom of the cell into which the electrolyte may settle. This can be avoided by nesting the current collecting link in a preformed dish which fills the dead space.

When the cell is increased in size to provide extra capacity problems may arise if the dimensions of the cell are not kept within certain limits. If the cell is made too tall the separators may no longer be able to retain the electrolyte at an adequate concentration at the top of the cell. We thus prefer to use an assembly in which the height of the separator is not greater than 200% or 150%, e.g., less than 100% or 70% or 50% of the free wicking height of the separator. The free wicking height is the height to which 1.28 sp. gr. sulphuric acid rises up a strip of the material when the material is suspended vertically above a bath of the acid with 1 cm. of the end of the strip below the surface of the acid and the strip and bath are enclosed in a sealed environment at 200C for 1 hour, so as to reach equilibrium.

Desirably the ratio of the positive and negative active masses combine in grams to the separator height is at least 13:1 and desirably at least 15:1 or 20:1 or 30:1 or greater.

The cells are desirably positioned in the battery so that these requirements of separator height in relationship to free wicking height are fulfilled, e.g. with prismatic cells a cell which would otherwise be too tall and thus liable to electrolyte displacement may be positioned on its side.

The invention may be put into practice in various ways and various specific embodiment of a cell in accordance with the invention and some modifications thereof will be described with reference to the diagrammatic drawings accompanying the provisional specification in which Figure 1 is a perspective view of an electrode/separator/electrode assembly for use in a wound cell in accordance with a first embodiment of the invention, Figure 2 is an underneath plan view of a cell in accordance with the present invention, utilising an assembly as shown in Figure 1, Figure 3 is a partial cross-section on the line III-III of Figure 2, Figure 4 is a view similar to Figure 3 showing a cell assembled in a battery box, Figure 5 is a diagrammatic plan view of an alternative form of battery assembly, Figure 6 is a diagrammatic part longitudinal cross section through the longitudinal axis of a single rechargeable cell in accordance with a second embodiment of the invention Figure 7 is a side perspective exploded view of the electrode and separator structure shown in Figure 6 prior to winding into a spiral, Figure 8 is a cross section on an enlarged scale of the separator material shown in Figures 6 and 7, and Figures 9 to 12 are scanning electron photomicrographs of the preferred separator material.

Figure 1 shows an enveloped positive strip electrode 10 enclosed at its bottom edge by a separator envelope 12 which extends up to the region of a current collector strip 11 integrally formed with the grid. It also shows a negative strip electrode 13 with an integral current collector strip 14 extending out beyond the bottom edge of the envelope 12. As can be seen in Figure 2, the inner end of the envelope 12 is preferably sealed whilst the outer end extends out beyond the outer end of the positive.

Both the strip electrodes are self-supporting lead alloy structures made by slitting. They are pasted with conventional active materials.

Figure 2 shows a central core 16 having a slot 17 to receive and grip the inner end of the electrode assembly; the notch 18 imparts a spring action to the core enabling the slit 17 to be flexed open.

The whole of the wound assembly is not shown, only the inner and outer free negative plate affording a free negative active material area 23 on its outer face. The active material is retained by means of a hydrophobic sintered semi-rigid porous polyethylene tube or wrapping 20 which is a tight fit around the wound electrode assembly, a free gas space 24 is provided by means of a spacer 21 of melt woven polyethylene (such as that sold under the Registered Trade Marks NETLON) having strands about 1.5 mm. thick spaced about 2 to 5 mm. apart but affording essentially only line contact with the retainer 20. The whole assembly is contained within a moulded polypropylene cell container 22.

Figure 3 shows a partial cross section of the cell shown in Figure 2. As can be seen the current collecting strip 14 of the negative electrode engages a toothed current collecting comb 27 which is nested in a plastic block 28 which fills the dead space at the bottom of the cell. The comb 27 has an integral lug 30 which passes out through the bottom wall 31 of the cell. The comb 27 is attached to the strip 14 by application of crimping pressure as shown for the positive comb 32 by the arrows X - X.

The comb 32 also has a lug 33 which passes out through the top wall 34 of the cell.

A vent collar 35 is located at the centre of the top wall. This is sealed until the cell is put into use or assembled into a battery.

Figure 4 shows a cell assembled in a battery box or in an outer cell container.

The cell is provided with a base 35 of moulded polymer material having an intercell connector or terminal base 36 e.g. of copper strip integrally moulded therein ready for spot welding Y to the lug 30 of the negative plate. An external lug can subsequently be provided in the recess 37.

The cell is also provided with a lid 38 incorporating a similar terminal arrangement for the positive electrodes.

The lid also incorporates a venting manifold 40 extending the length of the battery. The bottom of the manifold has a slot 41 formed in it wide enough for a rubber valve member 42 to be inserted into the manifold and secured to a boss 43 on the roof of the manifold. The dimensions of the lid 38, the manifold 40, the valve member 42 and the collar 35 are such that the top edge of the collar seals against the valve member 42 except at high pressures when the edges of the valve member 42 are lifted off the seating 35 when venting occurs.

Figure 5 shows an alternative arrangement in which cylindrical cells 45 in accordance with the invention are housed in assymmetrical essentially Y shaped solid shrouds 56, e.g., of hard rubber or other cheap essentially non-compressible material. Each cylindrical cell 45 is housed in its shroud 56 (in which it is desirably a push fit with its polarities in the same orientation, e.g., with its negative terminal by the waist of the Y).

In this arrangement, the terminals are on opposite sides of the cell, the negative lug 30 being led round the outside of the cell, between it and the shroud.

The battery is also provided with a lid similar to that shown in Figure 4 except that two vent manifolds are provided and three integrally moulded intercell connected strips as shown at 49, 47 and 48. The positive strips 47 and 48 are connected by cutting a slot 50 across above the strip 49 and inserting a cross link 51 and welding it to the exposed strips 47 and 48.

Clearly, if desired, the lids could be provided merely with apertures for the cell terminals at the correct spacings and longitudinal slots and the lugs could be used as the connectors and welded to each other or to separate connectors located in the slots.

The slots could then be filled with insulating resin.

The assembly has a battery casing similar to that shown in Figure 4 in which an open top and bottom metal (steel) box 60 is provided with a base 61 and lid 62 provided with appropriate apertures for terminals and vents and the lid and base are welded to the box or otherwise connected.

The material sold under the Registered Trade mark VYON F is a sintered polyethylene sheet material of 50% volume porosity and an air permeability of 70 to 100 cu. ft. air/min at 1" static water gauge. It is hydrophobic and not readily wetted by water. It is inert to 1.28 sp.gr. sulphuric acid. We prefer to use it at thicknesses of 0.03" to 0.04. It does not readily wick up sulphuric acid. VYON G (RTM) is made by granulating 3/16" thick VYON F into chips less than 5/15" by 3/16" and then sintering these chips into sheets 1/4" to 1/2". The material has an air permeability of 200 - 300 cu.ft./min at 2 to 3" static water gauge and a void volume of 70% to 80%.

The cell shown in Figure 6 consists of a spiral assembly wound from a single negative electrode 110 interleaved with a single positive electrode 111 sheathed in a separator 112.

This electrode assembly is enclosed within a cylindrical metal container 115 which is electrically connected to the negative electrode of the cell and thus affords the negative terminal of the cell. The container 115 is closed by a metal cover 116 which is insulated from the container 115 by a resilient insulating seal 117 and is electrically connected to the positive electrode 111 and thus affords the positive terminal for the cell.

The electrode assembly is wrapped in an outer band 120 of separator material and rests on a spiral disk of separator material which affords a reservoir 122 for electrolyte so as to reduce the risk of the cell being acid limited in use.

The electrode assembly has a central longitudinal channel 124 in which is located the bottom end of a vent assembly 126. The vent assembly has a central tube 125 open at the bottom end and closed at the top end by a resilient cap 127, the skirt 128 of which normally closes a hole 129 which passes through the wall of the top end of the central tube. A radial dish 130 extends out from the central tube 125 below the hole 129 and has an upstanding outer wall 132 which is a sliding fit inside the container 115.

An annulus 133 of separator material is located in the dish 132 and has the function of absorbing any acid spray which may be vented by the vent assembly 126 through the hole 129 during high pressure conditions in the cell, whilst permitting gas escape through a hole 135 in the cover 116.

To this end the annulus 133 may be treated, e.g., impregnated with an alkaline material e.g. Magnesium oxide or calcium carbonate.

Figure 7 shows the positive electrode 111 sheathed in a separator sheath 112 which is formed from a strip of material a little more than twice the width of the electrode strip. This sheath is sealed at the inner end 137 and along its top edge 138 between the current collecting terminals 140.

These terminals 140 are integral with a solid selvedge 141 along the top edge of the positive grid and are disposed logarithmically so that when the assembly is wound the terminals 140 are disposed radially in a straight line. They are connected together by a bar 143 and a lug 144 extends up through the dish 130 through the annulus 133 and up to the cover 116 of the container 115 to which it is connected e.g. by spot welding.

The negative electrode 110 is similarly provided with a selvedge 145 and logarithmically disposed lugs 146 offset from the lugs 140 so as to be disposed on a different radius when the assembly is wound. The lugs 146 are similarly connected via a bar 147 and lug 148 but to the container 115 rather than the cover 116.

The separator material used for the sheath 112, the reservoir 122, the bank 120 and preferably also the annulus 133 is shown in much enlarged cross section in Figure 8. It is made from polyester fibre by laying down as a non-woven bed of fibres e.g. as a air or water leaf followed by heating and possibly also pressure to temperatures such that the fibres fuse at their points of contact. The fibres are typically 25 to 150 mms, e.g. 80 to 100 or about 90 mms long and have a fused point of contact with other fibres every 1 to 10 e.g. 3 to 8 or about every 5 mm length of fibre. The diameters of the fibres are typically in the range 5 to 50 e.g. 10 to 30 or about 17 microns.

The material has a porosity of 70 to 75% (as measured by comparison of the density determined by Helium absorption) and an air permeability when dry of 1.67 = 10-2 litres per sec. per cm head of water per square cm.

It has an electrical resistance measured in 1.280 sp. gr. aqueous sulphuric acid of 3.0 milliohms per 4 square inches. It has a tensile strength in the range 0.25 to 0.62 kg.mm-2 as measured on a dry sample using a Houndsfield tensile testing machine, using a 5 cms long sample at a rate of extension of 3.18 mm per minute. It has an oxidation loss of 0.14% when a sample is exposed to oxidative conditions consisting of immersion in a 2.0% by weight potassium dichromate solution in sulphuric acid (1.050 S.G.) at 60OC for 24 hours.

It has a burst strength when dry on the burst test using Messmer burst testing equipment in excess of 850 KPa (Kilopascal - 1 pascal is 1 Newton per sq meter). It has the following pore size distribution as measured by mercury porosimetry 5% of the total porosity is provided by voids and the pores connecting such voids which are less than 25 microns in diameter. 12% is provided by voids and the pores connecting such voids which are between 25 and 50 microns in diameter. 40% is provided by voids and the pores connecting such voids which are between 50 and 100 microns in diameter. 12% is provided by voids and the pores connecting such voids which are between 100 and 200 microns in diameter and 4% is provided by voids and the pores connecting such voids which are above 200 microns.

The material as can be seen in Figure 8 is provided with channels 150 which are provided by regions which have been subjected to increased heat and pressure and which whilst subjected to increased heat and pressure and which whilst still porous are more dense than the remaining regions 151.

The compressed regions 150 provide for a much enhanced rate of liquid transport whilst the uncompressed regions 151 facilitate gas transport through the material. Referring to Figure 8 A is the width of the region 150, B the width of the region 151, C is the thickness of the region 151 and D is the thickness of the region 150. The ratio of B to A is preferably at least 1:1, 2:1 or 3:1 and preferably in the range 4:1 to 10:1 e.g. 5:1 to 7:1. A is preferably 0.5 to 2 cms. the thickness of the region 150, namely D, is preferably 0.05 to 0.5 mms whilst the thickness of the region 151, namely C, is preferably 0.3 to 2 mms, e.g. 0.5 to 1.0 mms. In our preferred separator C is 0.6 mms and D is about 0.1 mms and B/A is 4.

The separator material has a high rate of wicking up the compressed channels 150 which are preferably disposed vertically in the cell i.e. parallel to the longitudinal axis. Thus when the bottom edge of the material is immersed in 1.280 sp. gravity sulphuric acid at 20"C in an ambient atmosphere, the electrolyte rises 4 cms up the channel 150 in 15 seconds and 10 cms in 2 minutes. The acid permeates out sideways from the channel 150 into the regions 151 more slowly.

The invention will be further described with reference to six comparative examples in which the first three examples are in accordance with the invention in all aspects save the alloy composition and the second three are identical to the first three with the exception that the alloy composition is also in accordance with the invention.

Example 1 In a preferred cell the separator 112 has a size of 46 cms long, 5.5 cms high and 0.06 cms t 0.10 cms thick. They have a porosity of 50% and thus the pore volume of the electrodes, let us call it Y, is 22 cc.

The reservoir 122 is 1.0 cms high, 200 cms long and 0.06 cms thick. It has a porosity of 75% and thus the pore volume of the reservoir, let us call it Z, is 9.0 cc.

The band 120 has a height of 6.0 cms, a length of 13 cms and a thickness of 0.06 cms. It has a porosity of 75% and and thus the pore volume of the band 120, let us call it W, is 4.0 cc. Thus X + X + Z + W is 57.8 cc.

As explained in more detail below the volume of electrolyte in the cell is arranged to be at least X + Y + Z + W cc and preferably up to a small excess e.g. 10% excess over that value.

This ensures that the cell avoids being acid limited or electrolyte starved during use but the differential permeability of the separator enables gas recombination to occur in the cell.

Example 2 In an alternative arrangement the electrodes are made slightly thinner 0.09 cms. and longer 48 cms and the separator is made slightly longer 50 cms. Here X + Y + Z + W = 59.1 cc.

Example 3 In a further alternative the electrodes are made thinner still 0.08 cms. and longer 54 cms.

and the separator again longer, namely 56 cms. Here X + Y + Z + W = 62.3 cc.

The electrodes are made of a lead alloy containing 0.06% calcium and 0.10% tin and are made from sheet material 0.007 cms to 0.07 cms thick by slitting and pulling the material so as to expand the slits into diamond shaped holes. As mentioned above the electrodes have a continuous solid selvedge along one edge provided with integral lugs.

The length of the diamond is 0.7 cms. and its width 0.25 to 0.32 cms.

The electrode has 65 openings per sq. inch. The width of the strands between diamonds is 0.018 cms. to 1.4 cms.

We prefer to use this alloy rather than pure lead because it avoids the problems of creep and change in dimensions due to active material volume changes during charge/discharge cycles. Such stressed areas are very liable to corrosion with pure lead.

Examples 4, 5 and 6 Example 1, 2 and 3 were repeated with an alloy of 0.07% calcium and 0.7% tin. This has been found to have superior properties of strength, creep, hardness and corrosion resistance to the 0.06% calcium, 0.10% tin alloy used in Examples 1, 2 and 3.

The negative electrode is pasted with a negative active material containing lignin derived lignosulphonate material e.g. 0.1% to 0.8% e.g. 0.1% to 0.5% by weight based on the lead content of the active material, the lignin derived lignosulphonates being substantially free from interfering metal ions e.g. containing less than 0.2% of interfering triple valency metal ions and being derived from lignin by oxidation for example sodium or potassium lignosulphonate. The negative active material desirably also contains inorganic negative active material expander, e.g. barium sulphate, e.g. 0.1% to 0.5% by weight based on the lead content of the negative active material.

One particular material described as a purified lignosulphonate which has been found effective in the present invention is characterized by the following properties: (materials of this type are sold under the Trade Mark VANISPERSE). These lignosulphonates are derived from lignin by oxidation. Lignin is a by-product of the treatment of wood pulp and is obtained by the digestion of aqueous alkalis and alkaline bisulphites and is a by-product of paper production. The alkali soluble lignins appear likely to be chemically modified forms of the native lignin present in wood. e.g. oxylignins.

The lignosulphonate derivatives are made from the lignin by oxidation to lower the organically combined sulphur content. Molecular condensation and rearrangement is also thought to occur during this oxidation process.

Typical Analysis (moisture free basis) VANISPERSE C. B.

pH 3% solution in water Total sulphur as S% 2.4 Sulphate Sulphur as S% < 0.03 Sulphite Sulphur as S% < 0.03 CaO% 0.004 MgO% 0.002 Na2O% 9.9 Reducing Sugars None OCH3% 12.7 Physical Characteristics Usual Form Powder Moisture Content (Max.%H2O) 7.0 Colour Brown Bulk Density (Ibs/cu.ft) 35-40 Solubility in water (%) 100 Solubility in oils and most organic solvents (%) 0 Surface Tension 1% sol'n in Dynes/cm 51.4 Total Triple valency cations 0.03% It will be observed that the material is substantially sodium lignsulphonate with a significantly chemically analysable methoxy group content and substantial absence of sulphite groups. In addition the triple valency cation content is only 0.03%.

Triple valency cations such as Fe3+ are known to interfere with and reduce the performance of lead acid electric storage batteries.

As mentioned above lignosulphonic acids and lignosulphonate derived from lignin, a wood constituent, are used in the present invention. Lignin is thought to bind the cellulose fibres together in wood and-woody plants. It is a polymer which will vary somewhat in chemical make-up depending upon the plant source.

It is thought that the polymer comprises substituted phenyl propane monomers but the exact manner in which they combine to form the polymer lignin is not known. Thus it must be appreciated that a lignosulphonic acid or a lignosulphonate probably constitutes a group of closely related compounds rather than being a distinct chemical entity.

The term "lignosulphonic acid" refers to a material general available from the liquors produced by the sulphite, sulphate, soda ammonia base and other conventional processes for pulping wood. The term "lignosulphonate" refers to a salt of lignosulphonic acid.

Lignosulphonic acids are available in a variety of commercial forms and products, generally in the form of salt e.g. a sodium or potassium salt or mixtures of salts thereof. Both the free lignosulphonic acids and the salts thereof are within the scope of this invention. However, the higher water solubility of the lignosulphonates renders them more convenient and easy to handle; otherwise the free acid and salts are essentially the same for purposes of this invention.

Desirably additional liquor and amorphous silica are added to this negative active material, namely for each 1000 Kg of active material 265 mls of additional liquor per Kg of active material and 4.5 Kgs of amorphous silica, namely GASIL 23; this produces active material composition having a density of 3.8 gr/cc and the pasted electrode has a void volume of 58% and absorbs 22% of 1.280 sp.gr. sulphuric acid.

One specific negative active material composition N1 (without added liquor and silica) has the following composition.

Leady Oxide 1.091 Kg.

Vanisperse CB lignosulphonate 3.2 Kgs.

Barium Sulphate 5.5 Kgs.

Fibre 0.23 Kg.

Antioxidant (stearic acid) 0.57 Kg.

Carbon Black 1.8 Kgs.

Water 122 litres Sulphuric Acid (1.4 S.G.) 70 litres.

The oxide was placed in an August-Simpson paste mixer followed by the remaining dry ingredients: Vanisperse lignosulphonate, barium sulphate, fibre, antioxidant and carbon black in any order. The mixer was run for a few minutes until the dry powders were thoroughly blended.

The specified volume of water was slowly added with the mixer running and then the acid was added over a period of 15 minutes still with the mixer running. Mixing was continued for a further 5 minutes and was then complete.

Vanisperse CB content based on active material is 0.3%. Vanisperse CB is commercially pure sodium lignosulphonate and the lignosulphonate content is about 80%. Thus the lignosulphonate content of the negative active material is about 0.24%.

An alternative and preferred negative active material contains additional liquor and amorphous silica as mentioned above. Thus one preferred alternative paste, N2, has the same composition as N1 but has 4.9 Kgs. of GASIL 23 amorphous silica, which is added to the dry ingredients and 183 litres of additional water, and 106 litres of additional sulphuric acid (1.4 sp.gr.) This paste has a density of 3.8.

In another alternative paste N3, which is similar to N2 the silica content is 5.7 Kgs. and the additional water is 208 litres and the additional acid is 119.3 litres. This paste has a density of 3.5 gr cc and a void volume of 62% and acid absorbtion of 25%.

The weight of negative active material N2 is 43 grams in Example 1, 48 grams in Example 2 and 40 grams in Example 3.

The positive active material P1 is provided with the same amount of additional liquor and amorphous silica and is pasted on to the positive electrode in the same weight.

Specific examples of positive active materials are as follows: Pi Active material 1000 Kgs 40% lead 60% lead monoxide Water 297.9 litres Sulphuric acid (1.4 sp. gr) 156.1 litres Amorphous silica (gasil 23) 4.5 Kgs.

P2 As P1 except silica content is 5.2 Kgs.

Water content is 320 litres Acid content is 117.6 litres.

We find that using these pastes having densities of 3.9 and below especially 3.2 to 3.6 greatly enhances the rate of oxygen recombination at the negative electrode.

The presence of the amorphous silica with its large pore volume is also believed to assist in acid absorption by the plate since the increase is acid absorption appears to be greater than the increase in void volume.

The porosity values specified herein are determined by the well known mercury porosimetry or mercury intrusion method according to the general procedure described in "Pore size Distribution by Mercury Penetration" by Winslow and Shapiro in the ASTM Bulletin, February, 1959.

The method is as follows: The pressure required to force mercury into a pore is inversely proportional to the pore diameter. The volume of mercury forced into the pore is equal to the pore volume. The porosity of a sample is plotted against the pore size by observation of the volume of mercury forced into the sample at set pressures.

First the apparent volume of the sample is determined by geometry.

The machine used was a AMINCO machine.

The porosity as defined herein is the volume of mercury (expressed as a % of the total volume of the sample) which can be forced into the sample up to a pressure of 5,000 p.s.i.

Preferably the silica is added as amorphous silica of a micron or submicron particle size and a surface area in the range 50 to 700 especially 100 to 400 or around 200 to 300 sq.

metres per gram.

Desirably the amorphous silica (amorphous to X-rays) has a submicron ultimate particle size as measured by a Coulter counter, for example in the range 10 to 50 millimicrons though it may be agglomerated to larger average particle sizes for example of micron size such as 1-15 e.g. 5 - 10 microns or be of such larger ultimate particle size.

The amorphous silica can be added as such, for example, as the proprietory material GASIL (Trade Mark) e.g. GASIL 23 sold by Joseph Crosfield & Sons Ltd. and described in their Technical Publication No. 25 printed April 1969 (reference M598) or as the proprietory material AEROSIL (Trade Mark) e.g. AEROSIL R972 described in "Chemiker-Zeitung/Chemische Apparatur" 89/1965 pages 437 - 440.

GASIL is made by precipitation of a gel from sodium silicate solution with acid followed by drying, washing and hydrothermal or stream treatment to produce a material having a pore size of the order of 120 to 140 Angstoms with a surface area of 100 to 300 e.g. about 200 square metres per gram and a small particle size as described above e.g. 5 microns or less e.g. 3 to 5 microns. GASIL 23 has a maximum percentage weight loss of 12% at 1000"C, a pH of 6 to 8 as a 10% aqueous suspension, an oil absorption of 295 to 345 grams per 100 grams and the solids after ignition have a minimum silica content of 99.0%.

AEROSIL R.972 is believed to be pyrogenic silica made as described in British Patent Specification No. 1031764 which corresponds to French Patent No. 1368765 mentioned in "Chemische Zeitung" above.

AEROSIL R.972 has an average particle size of about 20 millimicrons and a surface area of 120 + 30 square metres per gram.

The disclosure of these three documents are incorporated herein by reference.

When silicas having a submicron particle size such as Cabosil M5 (R.T.M.) (trade name for a fumed or thermal silica sold in the United States of America and believed similar if not identical to Aerosil R972) are used at the 0.5 parts level a tendency has been observed for the pastes to harden too quickly and not remain workable overnight as is desirable. One should thus test the effect of the particular silica used in conjunction with the amount of extra liquids and the amount of silica used to achieve the desired balance of thixotropy and workability.

It is believed that with submicron particle size silicas this balance may be achieved by reducing the amount of silica used or increasing the amount of liquids or both.

Amorphous silica is characterised by the presence of silanol and hydroxyl groups i.e. free hydroxyl groups extending out from the surface of the silica polymer molecule which groups are capable of entering into a variety of relationships and bonds with appropriate groups or atoms of other molecules. In particular the OH groups can form hydrogen bonds with other OH groups in other molecules and espcially with water.

Thus whilst the present invention is not dependant on any particular theory it is thought that these silanol groups may be interacting with OH groups or water molecules present in the hydrated leady oxide and that this may account for the increase in strength. This possibly may also be influenced by the particular temperatures and times at which the plates are dried after pasting.

The preferred amorphous silicas for use in the present invention are characterised by the presence of micropores in their structure; these are preferably in the range 50 to 200 Angstroms particularly 100 to 150 especially 120 to 140 Agnstroms. The preferred silicas have a pore void volume of 0.1 to 5 ccs. per gram.

The electrolyte preferably has a specific gravity in the range 1.33 to 1.41 since we have found that the rate of gas recombination is higher in this region than it is above 1.41 or in the range of 1.33 to 1.29. The electrolyte volume we have found needs to be related critically to the capacity of the cell in order to achieve the best performance for the cell.

Thus if too much electrolyte is present in gas recombination may be suppressed but if too little is present the capacity of the cell will be restricted by insufficient electrolyte.

We thus prefer to use less than 10 mls of electrolyte per amphere hour of capacity and desireably 8.5 to 9.5 mls/Ahr.

The cell of this embodiment, shown in Figures 6 to 8, is assembled as follows.

The electrode supports are stamped out from the alloy sheet, expanded, pasted and then the positive is enclosed within the separator envelope of meldable fabric with the channels 150 transverse to the length of the electrode strip i.e. up and down in the assembled battery.

The edges of the sheath are then welded at the ends 137 and at the top edge 138 between the lugs 140 as indicated by the weld lines 160.

The sheathed positive is then laid over the negative and the assembly coiled so that the negative is on the outside face of. the coil. The coil is then wrapped in the band 120 of separator material and secured by the band being welded to itself where it overlaps as indicated by the weld line 161. (Figure 6).

A coil of separator material 122 is similarly wound or cut from a larger coil and its outer end secured by welding as indicated by the weld line 162 (Figure 6).

A similar coil 133 of separator material or glass fibre material having an annular shape with an open centre is also produced for location in the dish 130. A metal (or structural plastics) container 115 in which the electrode and separator assembly is a snug fit is provided. The coil 122 is placed in the bottom of the container, the electrode assembly slid in above it and the bars 143 and 147 with their upstanding lugs 144 and 148 burnt into place e.g. using a 98% lead 2% tin solder which we have found particularly effective with our preferred lead calcium tin alloys.

The vent assembly 126 is then placed in position with the bottom end 125 in the central opening 124 of the electrode assembly and the lugs 144 and 148 extending up through tight fitting holes in the dish 130. The annulus 133 is then slid into the dish 130 over the lugs.

The lug 148 is bent over and spot welded to the container 115. The cell is then flooded with electrolyte and electrolytically formed. The electrode assembly and reservoir 122 is then subjected to vacuum to draw of any gases in the pores of the structure and ensure that the pore volume X + Y + Z + W is filled with electrolyte.

The cell is then inverted and allowed to drain under gravity.

The cell then has the cover 127 placed on the vent assembly 126 and the lug 144 bent over and spot welded to the cover 116 which is secured in position in the top of the container.

The cell is then ready for use.

Figures 9 to 12 are photomicrographs of the preferred separator material described above for the sheaths 112 and 170. They are scanning electron photomicrographs. A scale is given beside each Figure.

The photomicrographs were prepared by taking a portion of the sheet and then directing a stream of electrons on to the surface at 45"C and collecting the electrons reflected from the surface also at 450C. The surface was first coated with a thin metallic reflecting layer as is conventional in preparing samples for electron photomicrography. It will be appreciated that the depth of focus of such photographs is very much greater than in optical photography and thus that in effect one is liable to see into the voids and cavities.

The material shown in Figures 9 to 12 is a melded polyester fibre fabric weighing 180 grams per square metre.

Figure 9 is a plan view at 115 fold magnification of an uncompressed region 151. The fibres are 17 to 20 microns in diameter. As can be seen the fibres are of substantial length e.g. of the order of 1200 microns such as the fibre 210, or 600 microns e.g. the fibre 211.

Thus the ratio of fibre diameter to fibre length is typically in the range 1:30 to 1:60. As can be seen substantial open spaces are left between fibres. These gaps are many times the diameter of the fibres.

Figure 10 shows a larger magnification (550 fold) view of an uncompressed portion 151 of the material.

Figures 11 and 12 show plan views (at 210 fold and 555 fold magnification) of one of the compressed regions 150. As can be seen the fibres are not fused into an impermeable sheet but are somewhat flattened e.g. to 30 or 40 microns across in the plane of the sheet and fused into solid regions. The gaps between fibres are now generally less than the cross-sections of the fibres.

WHAT WE CLAIM IS: 1. A sealed lead acid cell characterized in that it has electrodes comprising metallic supports which minimize the evolution of hydrogen and resist deformation under their own weight, the supports for the electrodes being in the form of a mesh or grid affording an integral current collecting strip or bar along at least one edge which will be the top or bottom edge of the structure when assembled in a cell and the supports for the electrodes being made of a lead-calcium-tin alloy containing 0.04% to 0.1 o by weight calcium and from above 0.5% to 1.0% tin, and which are separated by at least one layer of separator material, the support of the positive electrode or electrodes having positive active material deposited thereon, and the supports of the negative electrodes or electrodes having negative active material deposited thereon, and in which the capacity of the negative electrodes is arranged to be at least as great as the capacity of the positive electrodes, the thickness of each electrode is less than 3 mm, the thickness of the separator is in the range of 10% to 200% of thickness of the electrodes and the volume, E, of electrolyte in the cell in relation to the sum of the pore volume of the separators, X, and the pore volume of the positive and negative active materials, Y, is not greater than 2X + Y.

2. A cell as claimed in claim 1 in which the lead-calcium-tin alloy contains 0.6 to 0.9% tin and 0.06 to 0.09% calcium.

3. A cell as claimed in claim 1 in which the lead-calcium-tin alloy contains 0.7% tin and 0.07% calcium.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (3)

**WARNING** start of CLMS field may overlap end of DESC **. the surface also at 450C. The surface was first coated with a thin metallic reflecting layer as is conventional in preparing samples for electron photomicrography. It will be appreciated that the depth of focus of such photographs is very much greater than in optical photography and thus that in effect one is liable to see into the voids and cavities. The material shown in Figures 9 to 12 is a melded polyester fibre fabric weighing 180 grams per square metre. Figure 9 is a plan view at 115 fold magnification of an uncompressed region 151. The fibres are 17 to 20 microns in diameter. As can be seen the fibres are of substantial length e.g. of the order of 1200 microns such as the fibre 210, or 600 microns e.g. the fibre 211. Thus the ratio of fibre diameter to fibre length is typically in the range 1:30 to 1:60. As can be seen substantial open spaces are left between fibres. These gaps are many times the diameter of the fibres. Figure 10 shows a larger magnification (550 fold) view of an uncompressed portion 151 of the material. Figures 11 and 12 show plan views (at 210 fold and 555 fold magnification) of one of the compressed regions 150. As can be seen the fibres are not fused into an impermeable sheet but are somewhat flattened e.g. to 30 or 40 microns across in the plane of the sheet and fused into solid regions. The gaps between fibres are now generally less than the cross-sections of the fibres. WHAT WE CLAIM IS:

1. A sealed lead acid cell characterized in that it has electrodes comprising metallic supports which minimize the evolution of hydrogen and resist deformation under their own weight, the supports for the electrodes being in the form of a mesh or grid affording an integral current collecting strip or bar along at least one edge which will be the top or bottom edge of the structure when assembled in a cell and the supports for the electrodes being made of a lead-calcium-tin alloy containing 0.04% to 0.1 o by weight calcium and from above 0.5% to 1.0% tin, and which are separated by at least one layer of separator material, the support of the positive electrode or electrodes having positive active material deposited thereon, and the supports of the negative electrodes or electrodes having negative active material deposited thereon, and in which the capacity of the negative electrodes is arranged to be at least as great as the capacity of the positive electrodes, the thickness of each electrode is less than 3 mm, the thickness of the separator is in the range of 10% to 200% of thickness of the electrodes and the volume, E, of electrolyte in the cell in relation to the sum of the pore volume of the separators, X, and the pore volume of the positive and negative active materials, Y, is not greater than 2X + Y.

2. A cell as claimed in claim 1 in which the lead-calcium-tin alloy contains 0.6 to 0.9% tin and 0.06 to 0.09% calcium.

3. A cell as claimed in claim 1 in which the lead-calcium-tin alloy contains 0.7% tin and 0.07% calcium.