SHEET MATERIALS, THEIR PRODUCTION AND THEIR USE AS BATTERY SEPARATORS

Abstract: A sheet material that is suitable for use in alkaline batteries as a separator or interseparator is formed of about 30 to about 70 percent polyolefin synthetic pulp, from about 15 to about 65 percent alkali resistant inorganic filler and from about 1 to about 35 percent of one or more long fibres, and at least some, if not all of the fibre is a water swellable fibre and any remaining long fibre is a nonwater swellable fibre. The water swellable fibre during processing of the sheet forms a gel-like network when contacted by water which retains the filler and bonds the remaining materials together. The resulting sheet has increased tensile strength and alkali resistance and is especially useful in automated battery manufacturing processes.

Description: Sheet materials, their Production and their use as Battery Separators This invention is directed to a sheet material suitable for use in an alkaline battery system, preferably as a battery separator or inter-separator, and to a method of making the same. Alkaline batteries have become increasingly more popular because of their high energy density. As such, these batteries are increasingly used in applications normally reserved for the traditional lead-acid battery systems. In order to achieve extended battery life and efficiency in alkaline systems, the use of battery separators is required and the use of battery interseparators, as well, is preferred. The battery separators, when used for example in a nickel-cadmium battery, are located between the positive and negative plates so as to provide, (1) a separation between the electrodes of opposite charge, (2) an electrolyte reservoir, (3) a uniform electrolyte distribution across the electrode surface so as to permit uniform current density and (4) a space for electrode expansion. Interseparators are located between the separators and the plates and provide the same properties as the separators except that interseparators do not normally prevent dendritic growth. Separators and interseparators in such systems must be porous, thin, chemically inert to alkaline electrolytes and possess a high degree of wicking properties. By minimising the thickness of the separator and/or interseparator one can minimise the amount of electrolyte required and maximise the energy density of the battery. Further, by having a high degree of wicking properties, for example, 5cm/24 hours as determined by industry standards, one can maintain the electrolyte over the entire surface of the electrode, thereby further increasing the efficiency of the battery. Battery separators and interseparators used in alkaline batteries at present are commonly formed of polypropylene, polyamide and/or nylon non-woven sheets. Examples of separators and interseparators in use in alkaline systems today are shown in U.S patents 4,264,691 and 4,330,602. The separator/interseparator is formed of synthetic pulp, alkali resistant inorganic filler and a long fibre of polyester, polyacrylic, polyamide or polyolefin materials. The separator/interseparator can be formed by a standard paper-making technique. In EP 0064837 the reinforcing fibres can include polyvinyl alcohol or other chemically resistant fibres. A binder, e.g. polyvinyl alcohol size, can be applied. The resultant materials meet the desired requirements of thickness and wicking properties. The material however, often does not meet the required standards of tensile strength and filler retention necessary for the rapid development and use of alkaline batteries, especially for the automation of the manufacture of the batteries, particularly secondary alkaline systems, such as nickel-cadmium batteries. The present invention overcomes the problems inherent in the currently used separators and provides an inexpensive sheet material with the desired tensile strength, chemical inertness, thickness and wicking properties and which is usable in automated assembly processes for forming alkaline batteries. A sheet material according to the invention is alkali resistant and is formed from a composition of from about 30 to about 70 percent polyolefin synthetic pulp, from about 15 to about 65 percent alkaline resistant inorganic filler and from about 1 to about 35 percent of one or more long fibres and at least some of the long fibres are water swellable and when water swollen become gel-like and sticky and bind at least some of the remaining ingredients together. The sheet materials of the invention can be constructed for use wherever a thin, porous, alkali resistant sheet with high tensile strength is required. They are of particular value in batteries, especially in alkaline batteries. Preferably they are used as separators or interseparators in alkaline battery systems. For ease of description the invention is described below primarily with reference to such separators and interseparators. The sheet materials of the invention can have excellent tensile strength, for instance above 400lbs/in² (28kg/cm²), wicking properties, for instance at least 5cm/24hours, and alkali resistance. All measurements stated in percent in this application, unless otherwise stated, are measured by weight based upon 100% of the finished product weight. Thus, for example 30% represents 30 weight parts out of every 100 weight parts of the finished product. The synthetic pulp useful in the present invention may be a polyolefin of short fibres having a fibre size and shape similar to that of cellulose pulp. Such synthetic pulps are described in U.S. patents 4,264,691 and 4,330,602, to which reference should be made. The fibre length of the synthetic pulp is preferably from about 1 to 4 millimeters. The preferred pulp is a polyethylene based pulp. Other pulps are equally useful and may be made of other polyolefins such as polypropylene. Pulp fibres with a high degree of branching or fibrillation are most preferred in the present invention. The alkali resistant inorganic filler can be any particulate material which is chemically inert to alkaline electrolytes. Alkali resistant inorganic fillers suitable for use in the present invention include for example, titanium dioxide, alumina, calcium oxide, calcium hydroxide, calcium titanate, potassium titanite, magnesium hydroxide, magnesium oxide or zirconium hydroxide and admixtures thereof. Of course, any other alkali resistant filler, which is compatible with the other ingredients used in the sheet of the present invention and known to one skilled in the art can be used as well. A preferred filler is potassium titanite. Another preferred filler is titanium dioxide. The filler preferably has a particle size of from about 0.001 to about 1 microns, a surface area of from about 5 to about 200 square meters per gram and a pore volume of from about 0.01 to about 1 cc per gram. The long fibres used in the present invention are formed of synthetic polymers, and some or all of the long fibres are water swellable. The swellable fibres are fibres that swell highly in water during manufacture of the sheet and become gel like and sticky. Preferred swellable fibres are formed of swellable polymers of vinyl alcohol such as a vinyl alcohol polymer or a copolymer of a polyvinyl chloride (PVC) and a polyvinyl alcohol or a grafted copolymer comprising a vinyl chloride backbone grafted with a vinyl alcohol polymer. Such fibres are commercially available. A commercially available example of a vinyl alcohol polymer water swellable fibre is MEWLON SML by Unitika Kasei, Ltd. An example of a commercially available polyvinyl chloride/polyvinyl alcohol copolymer is sold by Kohjin Co. The long fibres may consist solely of the swellable fibres but preferably they also include relatively non-swellable fibres and so preferably the long fibres are a blend of a first, swellable, fibre type and a second, non-swellable, fibre type. This second type should be compatible with the first and preferably is also based on a vinyl alcohol polymer, for instance a vinyl alcohol polymer that has been cross-linked, e.g., with formaldehyde, to render it relatively non-swellable. The second long fibre type is preferably a nonwater swellable cross-linked PVA, such as MELON F, by Unitika Kasei, Ltd., although other nonwater swellable fibres such as polyester, polyacrylic, polyamide, polyolefin or mixtures thereof, can be used. The long fibres, swellable and nonswellable, should have a denier of from about 1 to about 12 and a length of at least about 6mm. It is usually below 37mm, preferably below 25mm. The total amount of long fibres can equal the amount of pulp used. Preferably, the total amount of long fibres is approximately 50% of the amount of synthetic pulp. Also the amount of water swellable fibre is preferably equal to or less than the amount of nonwater swellable fibres. However they must of course be present in an amount sufficient to give a beneficial improvement and so they generally need to be present in an amount of at least 0.5% of the total product. Often there is 0.5 to 17.5% of each type of long fibre. It has unexpectedly been found that the use of the water swellable long fibres, especially in combination with non-swellable long fibres, results in a sheet material which has superior tensile strength and filler retention, even without the use of traditional retention aids. While the applicant does not wish to be bound to any one theory of invention, it is thought that the following is an explanation as to the operation of the present invention. At least the surface of the water swellable long fibre becomes gel-like and sticky when in contact with water during the formation of the sheet of the present invention. This gel-like phase of the fibre acts as a binder or an adhesive, binding all of the remaining ingredients of the sheet together. Further the gel-like phase binds the filler to its surface thereby retaining an increased amount of filler that would normally be lost during the dewatering of the sheet material. Upon drying, the water swellable material returns to its previous state but is now intermeshed and bonded to the other components which increases the tensile strength of the finished sheet. It is also believed that additional bonding between the swellable fibre and the other components occurs where the optional second fibre and the water swellable fibre are both PVA fibres, due to their compatibility. Sheet material formed in accordance with the present invention are porous materials having a median pore diameter of less than 10 microns (µm) and a maximum pore diameter of no more than about 35 microns (µm). The process by which the sheet of the present invention is formed may be similar to that described in U.S. patents 4,264,691 and 4,330,602 to which reference should be made. A typical process is carried out on normal paper-making machinery, such as a rotoformer or Fourdinier paper machine. A slurry is formed in a conventional paper-making pulper first by charging the synthetic pulp with water and pulping the material until it is thoroughly dispersed. Various dispersants may be added if necessary or desired, or more preferably the pulp may optionally contain a dispersant. One or more fillers are then added and mixed in the pulper until thoroughly dispersed. The pulper content is then discharged into the chest of a rotoformer or a Fourdinier paper machine. A water swellable long fibre is added to the chest and mixed for a sufficient amount of time so as to allow the fibre to swell. Preferably the slurry is warmed to room temperature or greater to aid in the swelling of the fibre. Next a nonwater swellable fibre if used is mixed into the chest. After thoroughly mixing the components in the chest, ground alum, (aluminium sulphate) preferably iron free, is added. The aqueous slurry is then transferred from the chest to a dilution box upstream of a web forming headbox. There, the mixture is diluted with water until the solids concentration is less than 5 percent preferably less than 1 percent. The mixture is then transferred to the headbox and a web is formed on the rotoformer or Fourdinier machine. A lump breaker operating at 1.4 to 5.6kg/cm² smoothes the upper surface of the web. The web is transferred from the rotoformer or Fourdinier machine to an oven and/or one or more drying cans where the web is dried. During the drying or subsequent thereto, the web may optionally be heated to a temperature of from about 125°C to 150°C to allow for the partial fusing of the synthetic pulp fibres. The thickness of the resultant web is directly related to the rate at which the slurry is deposited on to the web forming apparatus, the solids concentration at that moment and the speed of the web forming apparatus. The sheet material should have a thickness of less than 20 mils (0.5mm). Preferably the resultant sheet material should be less than 12 mils (0.3mm), requiring therefore that the deposition of the slurry be at a grammage of less than about 120 grams per square meter (gm/m²), preferably 50 to 120 gm/m². Of course, should a thicker sheet material be desired, one could easily increase the deposition grammage until a sheet of desired thickness is achieved. The dried web may be calendered at sufficient pressure and temperature to form a sheet having a thickness of less than 12 mils (0.3mm) preferably 5 to 10 mils (0.12 to 0.25 mm). The use of a retention aid is not required in the present invention as it has been found that the water swellable long fibre attracts and retains the filler to its surface so that the amount of filler lost during drying is substantially reduced. One could use retention aids in the process to further reduce the loss of filler during drying. If use, preferably the slurry is treated with an ionic retention aid such as a cationic polyacrylamide and then an anionic polyacrylamide retention aid. An example of a cationic acrylamide useful in this invention is RETEN 210, a product of Hercules, Inc. A suitable anionic retention aid is RETEN 421 or 521, an anionic acrylamide copolymer of Hercules, Inc. Typical concentrations are 0.04% in water at 600 to 800ml/minute for the cationic retention aid and .025% in water at 600 to 800ml/minute for the anionic retention aid. Other aids, such as surfactants to improve the electrical resistance of the sheet material, and wetting agents are also usable in the present invention, so long as they do not have an adverse effect on battery performance or life. The following examples are given for illustrative purposes only and are not meant to be a limitation on the present invention. All percentages are by weight of the finished product unless otherwise stated. Example I 30 percent of a commercially available short fibred synthetic polyethylene pulp (PULPEX, Grade EA, by Hercules, Inc.) was charged into a papermaking pulper with water. After the pulp is thoroughly dispersed, 45 percent of titanium dioxide is added and pulped for 10 minutes. The pulper contents are then discharged into the chest of a rotoformer machine and 10 percent of a waterswellable long fibre, here a polyvinyl alcohol fibre (MEWLON SML by Unitika Kasei, Ltd.) of 1.0 denier is mixed into the chest. The water temperature is maintained between 20°C and 30°C until the fibres have swelled and have formed a gel-like surface. Then 15 percent of a nonwater swellable polyvinyl alcohol fibre (MEWLON F by Unitika Kasei, Ltd.) was added. After thoroughly mixing the chest, 2 percent of ground alum (aluminium sulfate, preferably iron-free) was added. The slurry was then transferred to a dilution box upstream from the rotoformer headbox. The mixture is diluted with water until the solid concentration is less than 0.1 percent. The dilute mixture is then transferred to the headbox and a web is formed on the rotoformer. A lump breaker operating at 80psi smoothes the top surface of the web. The web is then transferred from the rotoformer to one or more drying cans and after drying is wound on to a take up reel. The resultant web has the following properties: (A) Tensile strength (machine direction) - 1363psi (9.4×10³KPa)(95.8kg/cm²) (B) Grammage - (grams/m²) - 90 (C) Maximum pore size - 25µm (D) Percent porosity - 65 (E) Thickness - 8 mils (0.2mm) (F) Wick rate (cm/24h.) - greater than 16 Comparative Example I A sheet material was made in accordance with Example 1 of U.S. patent 4,330,602, containing 47.5 percent polyethylene pulp, 47.5 percent titanium pulp, 47.5 percent titanium dioxide, 5 percent nonwater swellable long fibre of polyethylene terephthalate, 2 percent alum and ionic retention aids. The resultant sheet has the following properties: (A) Tensile strength - 470 psi (33 kg/cm²)(3.23×10³KPa) (B) Grammage (gm/m²) - 90 (C) Maximum Pore Size - 15µm (D) Percent Porosity - 62 (E) Thickness - 8 mils (0.2mm) (F) Wick Rate (cm/24h.) - greater than 16 As one can see from the examples above, the present invention has a tensile strength which greatly exceeds that previously available in a sheet material for alkaline battery systems. Example II The procedure of Example I was carried out except as follows: a cationic acrylamide containing retention aid (RETEN 210 by Hercules, Inc.) was added to the dilution box at a concentration of 0.05 percent in water at 600 ml/minute. An anionic acrylamide retention aid (RETEN 521, by Hercules, Inc.) was added in the dilution box three feet downstream of the first retention aid at a concentration of 0.025 percent in water at 800 ml/minute. The resultant sheet had properties similar to those of Example I and was found to have retained approximately 3% more filler than the sheet of Example I. Example III The procedure of Example I was carried out except as follows: the nonwater swellable polyvinyl alcohol fibre was replaced with 15 percent of a nonwater swellable polypropylene long fibre (HERCULON 153, by Hercules, Inc.) The resultant sheet had the following properties: (A) Tensile strength 812.5 psi (57.1kg/cm²)(5.6×10³KPa) (B) Grammage (gm/m²) - 90 (C) Maximum pore size - 25µm (D) Percent Porosity - 65 (E) Thickness - 8 mils (0.2mm) (F) Wick rate (cm/24h.) - greater than 16

Claims: A sheet material that is suitable for use in an alkaline battery system comprising from about 30 to about 70 weight percent of the sheet material of polyolefin synthetic pulp, from about 15 to about 65 weight percent of the sheet material of an alkali resistant inorganic filler, and from about 1 to 35 weight percent of the sheet material of long synthetic fibres characterised in that at least some of the long synthetic fibres are water swellable and have been swollen in water to become gel-like and sticky to bind at least some of the remaining ingredients together. A sheet material according to claim 1 wherein the long fibres comprise first swellable fibres and second non-swellable fibres. A sheet material according to claim 2 wherein the amount of water swellable long fibre is equal to or less than the amount of nonwater swellable long fibre. A sheet material according to claim 2 or claim 3 comprising 0.5 to 17.5% of swellable long fibres and 0.5 to 17.5% of non-swellable long fibres. A sheet material according to any of claims 2 to 4 wherein the first fibres are swellable vinyl alcohol polymer fibres and the second fibres are vinyl alcohol polymer fibres cross-linked such that they are substantially non-swellable. A sheet material according to any preceding claim wherein the amount of long synthetic fibre is equal to or less than the amount of synthetic pulp. A sheet material according to any preceding claim in which the long swellable fibres comprise fibres of polyvinyl alcohol, a copolymer of polyvinyl alcohol and polyvinyl chloride, and a graft copolymer comprising a vinyl chloride backbone grafted with a vinyl alcohol polymer. A sheet material according to any preceding claim wherein the long synthetic fibres have a denier of about 1 to about 12 and a length of from about 6 to 37mm. A sheet material according to any preceding claim having a tensile strength of at least 28kg/cm². A sheet material according to any preceding claim wherein the polyolefin pulp comprises polyethylene and/or polypropylene, the filler comprises titanium dioxide, alumina, magnesia, potassium titanite, zirconium hydroxide, magnesium hydroxide or a mixture thereof; and the nonwater swellable long fibre comprises non-swellable fibres of vinyl alcohol polymer, polyester, polyacrylic, polyamide, polyolefin or mixtures thereof. A sheet material according to any preceding claim in the form of a battery separator or interseparator. An alkaline battery comprising one or more positive electrodes, one or more negative electrodes, an alkaline based electrolyte solution and a separator or interseparator, characterised in that the separator or interseparator comprises a sheet material according to any preceding claim. A method of producing a sheet material according to any of claims 1 to 11 comprising the steps of: mixing the polyolefin synthetic pulp with water, adding the inorganic, alkali resistant filler and mixing thoroughly to form a slurry, transferring the slurry to a chest of a paper-making machine and adding the long synthetic fibres, diluting the slurry with water to a solids concentration of less than about 5 percent, transferring the slurry on to a web forming device, forming a web and drying the web to obtain the sheet material, characterised in that at least some of the long synthetic fibres are water swellable and the slurry is held at room temperature or greater to allow the water swellable long synthetic fibres to swell before transferring the slurry to the web forming device.

Inventors: CHOI, WAI MING
Applicants: W.R. GRACE & CO.-CONN. (A CONNECTICUT CORP.)
Application year: 1987
Main classification: H01M2
IPC codes: H01M2