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WO1998007204A1 - Separateurs en papier couche pour cellules electrolytiques - Google Patents

Separateurs en papier couche pour cellules electrolytiques Download PDF

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Publication number
WO1998007204A1
WO1998007204A1 PCT/GB1997/002148 GB9702148W WO9807204A1 WO 1998007204 A1 WO1998007204 A1 WO 1998007204A1 GB 9702148 W GB9702148 W GB 9702148W WO 9807204 A1 WO9807204 A1 WO 9807204A1
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WO
WIPO (PCT)
Prior art keywords
separator according
starch
additive
cells
hydro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB1997/002148
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English (en)
Inventor
Christopher Fred Randell
Neal Charles White
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ever Ready Ltd
Original Assignee
Ever Ready Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB9616703.6A external-priority patent/GB9616703D0/en
Priority claimed from GBGB9625325.7A external-priority patent/GB9625325D0/en
Priority claimed from GBGB9711646.1A external-priority patent/GB9711646D0/en
Application filed by Ever Ready Ltd filed Critical Ever Ready Ltd
Priority to AU38577/97A priority Critical patent/AU723792B2/en
Priority to EP97935681A priority patent/EP0947017A1/fr
Publication of WO1998007204A1 publication Critical patent/WO1998007204A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/22—Immobilising of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to electrochemical cells having coated paper separators, wherein the separator coating comprises a starch and an additive, as well as to such separators .
  • the separator and the coating of the separator can very substantially affect the performance and safety features of a cell, to the extent that the cells are even improved in the fresh SCA (Short Circuit Amperage) test.
  • Separators having coatings comprising the above ingredients result in dry cell batteries which perform markedly better than those comprising standard ingredients, m many standard battery tests. This is particularly so in regard to abuse conditions.
  • abuse tests There are many abuse tests, but we have devised two tests to assay leakage under abuse conditions (the HDCT and LDCT tests, described below) .
  • the HDCT test assays those conditions which might be encountered where a flashlight was left in the "on” condition over a period of time, even after the battery had, to the user, gone “flat”.
  • the LDCT test simulates the conditions experienced by a battery in, for example, a clock. The advantage of these tests is that they can be performed relatively quickly, and t is not necessary to wait for a year or so to establish whether the battery will perform m a clock, for example, without leaking.
  • the present invention provides a coated paper separator for an electrochemical cell, the coating comprising a starch, characterised in that cationic starch constitutes a majority of the starch component of the separator coating.
  • the present invention provides a coated paper separator for an electrochemical cell, the coating comprising a starch and an additive, characterised in that the starch is a cationic starch and the additive has a hydro- lipophilic balance of less than 17.
  • a particularly advantageous type of additive is generally classifiable as a surfactant, and is particularly preferably a polyoxyalkylene, nitrogen containing compound.
  • a starch such as Vulca 90 and a polyoxyethylene amine such as Crodamet C20.
  • Crodamet C20 has an average of 20 oxyethylene units per amine and has an alkyl group on the amine averaging about twelve carbon atoms. Crodamet C20 has an HLB of 17.
  • any additive having an HLB of less than 17 provides a cell which is superior:- a) to the cells of the art with regard to reduced leakage probability, and b) to cells having cationic starch in combination with Crodamet C20.
  • any additive having an HLB of less than 17 is useful in the separators of the present invention, but it will be appreciated that additives having an HLB of 14 or less are preferred, as these allow the production of cells having substantially identical performance with cells of the art, but which are far less likely to leak under abuse conditions .
  • HLB high-density polystyrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-sulftyrene, polystyrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-st
  • the HLB of an additive results from the balance between such hydrophobic constituents as alkyl chains, and such hydrophilic components as oxyethylene units.
  • the average alkyl chain length is 12
  • the average number of oxyethylene units is 20, effectively corresponding to two decameric polyoxyethylene units substituting an amine which is further substituted by a C 12 alkyl side chain.
  • Crodamet C20 many compounds may make up the generic product known as Crodamet C20.
  • Crodamet C20 is largely based on coconut alkyl groups which have, as stated above, an average chain length of 12.
  • Crodamet T5 which contains five oxyethylene groups, has an HLB of 12. Accordingly, it is generally desirable to lengthen the average alkyl chain, so that we have found that tallow provides a useful alkyl length, having an average of about 18 carbon atoms.
  • Ethylan TT203 is an amine having two oxyethylene substituents and an alkyl substituent having an average length of 18 carbon atoms, and this has an HLB of 5.
  • Crodamet T5 (having five oxyethylene units) is preferred.
  • the alkyl chain length and the number of oxyethylene units can be varied in any suitable manner in order to obtain an additive with a desired HLB.
  • additives having a relatively low HLB it is preferred that these additives should be non-ionic and, for the purposes of the present invention, non-ionic additives are preferred.
  • cationic starch relates to any starch which has, in its molecular structure, at least one cation, on average, per starch molecule in si tu .
  • Cationic starch is well known in the art and is disclosed, for example, in "Starch, Chemistry and Technology (Academic Press, Inc., Eds. Whistler, R. , Bemiller, J. , and Paschalle, E., second edition, 1984) .
  • cationic starches can be prepared as disclosed in GB-A-2063282 and US-A-4613407, both of which are incorporated herein by reference.
  • US-A-4613407 describes the use of a combination of cereal and tuber cationic starches as a wet-end cationic additive for the manufacture of paper. Many uses are generally suggested for cationic starch in both references, but no use had previously been suspected for electrochemical cells.
  • cationic starches may be prepared by solubilising normal starch in water and exposing said starch to a suitable cationising agent under alkaline conditions.
  • the agents illustrated in GB-A-2063282 are lower alkyl halohydrins and lower alkyl haloepoxy compounds, and these are suitable to yield cationic starches with viscosities higher than 1000 and even 2000 Brabender units, measured at a concentration of 5% v/v in water.
  • a generally preferable level of nitrogen content is between 0.2 and 2% w/w by dry weight of starch, although this can go up to as far as 2.8%.
  • the only real ceiling is the practical limit imposed by chemical and cost considerations .
  • the separator coating be made substantially as is known in the art, but incorporating cationic starch in place of some or all of the starch component of the coating.
  • Preferred paper and other ingredients are generally as described herein.
  • the cationic starch should form a majority of the starch component of the coating for the separator and, in general, we prefer that it should form all of the starch component, although it may occasionally be desirable to incorporate another component, such as Vulca 90.
  • the cationic starch of the present invention there is no restriction on the nature of the cationic starch of the present invention.
  • the cationic starch should not be readily soluble in water, in which case we prefer that it should not be at all soluble in water (at least cold water) , and that it should not expand in the presence of water.
  • the cationic starch should be at least partially cross-linked. Uncross-linked cationic starches do not perform satisfactorily, although there does not seem to be much difference in the performance of highly cross-linked starches and moderately cross-linked starches.
  • the starch may be any suitable starch.
  • suitable starches are known, and include potato, corn, wheat and tapioca starch.
  • the nature of the cations is also not important, although it is generally preferred that the substance should not be toxic, for environmental reasons.
  • Suitable cations are the sulphonium, phosphonium and ammonium ions, of which the latter are preferred, and these can be introduced into the starch using suitably alkylated molecules .
  • Suitable alkyl amines will tend to result in the starch being substituted by trialkyl ammonium groups under the acidic conditions present in a zinc carbon cell.
  • the cationic starch used is in the form of, for example, dialkylamino substituted starch
  • this precursor product may be converted into the cationic product by suitable treatment with acid, and this may be effected either in si tu , or prior to incorporation of the separator into the cell.
  • a particularly preferred cationic starch of the present invention is a potato starch made by Roquette (Roquette Freres, 4 rue Patou, F-59022 Lille Cedex, France) under number LAB 2273, but other manufacturers also make appropriate grades of cationic starch.
  • Separators generally require the use of gellants in their manufacture.
  • the various soluble starch gellants and natural gums used to manufacture separators all appear to decompose during storage.
  • etherified cellulose derivatives appear to be stable in aqueous solutions of zinc chloride, and these are particularly advantageous for use in the present invention.
  • Suitable examples of gellants for use in the present invention include: Tylose MH200K (Trademark of Hoechst) , Tylose MH50, Culminal MHPC100 (Trademark of Aqualon) and Courtaulds DP 1209.
  • Particularly preferred etherified cellulose derivatives should ideally swell and gel substantially immediately and remain stable in the presence of water over long periods, such as described in PCT/GB96/01318, and suitable etherified celluloses include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose (including salts, such as the sodium salt) , hydroxyethyl cellulose, ethylhydroxyethyl cellulose, methylhydroxyethyl cellulose, 2- hydroxypropyl cellulose, methylhydroxypropyl cellulose and 2- hydroxypropylmethyl cellulose.
  • viscosity is an important factor in choosing a gellant. If the separator mix is outside certain viscosity limits, typically in the region of 3000 to 70000 cP (3 to 7.0 Pa.s), undesirable results and poor cells are usually obtained. Below 3000 cP (3 Pa.s), the mix is often so liquid that it soaks straight into the paper, which can lead to the tearing of the paper, for example. Above 70000 cP (70 Pa.s), the mix is generally too thick to spread onto the paper satisfactorily.
  • an etherified cellulose derivative having a viscosity of between about 20 cP (0.02 Pa.s) and about 300 cP (0.3 Pa.s) .
  • the viscosity of a substance is defined in terms of a 2% w/v aqueous solution of that substance at 20°C at a neutral pH. Ideally the viscosity is between 50 and 100 cP (0.05 and 0.1 Pa.s).
  • the additives useful in accordance with the present invention are suitably nitrogen containing compounds of any type that is suitable to be substituted by one or more polyoxyalkylene groups .
  • amine and ammonium compounds are preferred, especially the amine compounds, other compounds which have substitutable nitrogen bonds are also suitable, such as carbamoyl, diazo and aci-nitro compounds.
  • the individual alkylene moieties in the polyoxyalkylene substituents may be the same or different, but will generally be the same owing to the methods of manufacture employed for such compounds .
  • Useful alkylene groups tend to be restricted to the ethylene and propylene groups, but the propylene groups are not as good as the ethylene groups at preventing gassing, so that polyoxyethylene nitrogen containing compounds are preferred, especially the polyoxyethylene amines.
  • any given polyoxyalkylene moiety it is possible for any given polyoxyalkylene moiety to contain a mix of lower alkylene groups, such as methyl, ethyl and propyl. Where this is the case, then we prefer the average alkylene length to be two, or close to two, carbon atoms.
  • this is substituted by at least one polyoxyalkylene group and one saturated or unsaturated alkyl group.
  • This group is preferably an alkyl or alkenyl group. There is generally no advantage to alkynyl groups, although these are also envisaged.
  • the group may be straight or branched and may be substituted by one or more substituents, such as hydroxy groups and halogen atoms, but it is generally preferred that the alkyl group is unsubstituted.
  • the level of saturation is ideally complete or there are only one or two carbon-carbon double bonds. It is also preferred that the alkyl group should be straight chain and contain from 1 to 30 carbon atoms, provided that the compound has an HLB of less than 17.
  • Compounds of the present invention may also contain more than one amine centre, in which case it is preferred that the individual amine groups are bridged by alkylene groups, preferably a short chain alkylene group, such as a trimethylene group .
  • the present invention provides separators comprising such compounds in accordance with the teaching of PCT ⁇ GB96 ⁇ 01319, which is incorporated herein by reference.
  • an alkyl chain is disclosed in PCT ⁇ GB96 ⁇ 01319, then this may be substituted with an unsaturated chain, provided that at least one alkyl is replaced by an unsaturated chain.
  • the chain length of the polyoxyalkylene group is not particularly important to the present invention, provided that the HLB is less than 17, but we prefer that the chain length should be between 1 and 5, preferably with an average length of between 1 and 3 and especially around 2 or 3.
  • compounds derived from tallow amines are preferred, and tallow alkyl groups contain between around 18 carbon atoms.
  • the most preferred compounds of the present invention are mono- and di- amines wherein the free alkyl group has around 18 carbon atoms, the side chains are polyoxyethylene substituents having an average of 1 or 2 oxyethylene units each and, where the compound is a diamine, then the link between the two amine centres is trimethylene.
  • the preferred compounds for use in the present invention are currently derived from tallow, and this has the following composition, by comparison with coconut, where chain length is the number of carbon atoms :
  • any suitable paper may be used in accordance with the present invention, by which is meant any paper suitable for use as a separator.
  • most papers used in conventional separators are from a single source of pulp and, while these papers are relatively cheap to manufacture, they tend to perform poorly in a number of tests. Nevertheless, we have established that it is possible to produce papers from a single source of pulp which perform well in tests, and such papers are characterised by their ability, at a temperature of about 20°C, to absorb a 50 ⁇ l droplet of water in a period of between four and fifteen minutes. More preferably, this period is between five and fifteen minutes and is particularly preferably between five and ten minutes .
  • the paper absorbs the droplet of water in less than four minutes, then the density of the paper tends to be too low, and poor results may be obtained. If the paper absorbs the droplet in greater than fifteen minutes, then this causes practical problems during manufacture, as the individual cells need to be voltage tested soon after assembly, and the delay in absorbing the electrolyte from the mix would mean that there would be an unacceptable storage time before the cells could be tested.
  • the characteristics of the papers which have the necessary absorption tend to be those of high beat and high density. Beating is performed on the pulp prior to formation of the paper, and the degree of beating can be measured by the use of the "Canadian standard freeness tester". The test is T 227m-58 of the Technical Association of the Paper and Pulp Industry and is described, for example, in “A Laboratory Handbook of Pulp and Paper Manufacture” (Auth. J. Grant, Pub. Edward Arnold, 2nd Ed. 1961, pp. 154 et seq. ) .
  • one particularly preferred paper of the present invention is made by Cordier (product code COK-70) and has a density of 0.64g/cm 3
  • another particularly preferred paper of the present invention is made by Munksjo (product code 114440) and has a density of 0.76g/cm 3 .
  • SDMF Sibille Dalle 58060
  • the Cordier papers are available from Piefabrik Cordier GmbH, Pfalz, Germany,* the Sibille Dalle papers are available from Sibille Dalle, Vitry sur Seine, France; the Munksjo papers are available from Munksjo Paper AB, Jonkpong, Sweden; and the Tervakosko papers are available from Oy, Tervakoski, Finland.
  • Papers having a density of less than about 0.6g/cm 3 tend to yield poor results in the tests, whilst papers with densities in excess of about 1. Og/cm 3 tend to adsorb in greater than 15 minutes in the water droplet absorption test.
  • Another advantage of using cationic starches is that the quality of manganese dioxide is not as important as in other cell constructs. This is a major advantage, as manganese dioxide is a major expense in the manufacture of dry cells, and great savings can be made if, for example, relatively cheap sources of electrolytic manganese dioxide (EMD) can be used. At present, such low grade material can only be used if it is combined with higher grade material in order to avoid leakage, but this is no longer necessary if cationic starches are used in accordance with the present invention. The present invention now makes it possible to use cheaper materials, such as are available from the People's Republic of China, for example.
  • EMD electrolytic manganese dioxide
  • the present invention also provides electrochemical cells comprising separators of the present invention.
  • a coating mix suitable for the manufacture of coated separators of the present invention comprising cationic starch.
  • Typical cells in which the separators of the present invention can be used include primary and secondary zinc carbon cells, including those cells known as Leclanche and zinc chloride cells, as well as alkaline cells.
  • the electrolyte in zinc carbon cells is typically as follows: Leclanche electrolyte - 5-20% zinc chloride, 30-40% ammonium chloride, remainder water; zinc chloride electrolyte - 15-35% zinc chloride, 0-10% ammonium chloride, the remainder water.
  • Cells may have any suitable configuration, such as round, square or flat.
  • HDCT High Drain Continuous Test
  • LDCT Low Drain Continuous Test
  • the High Drain Continuous Test is intended to simulate abuse conditions, such as might be found in leaving a flashlight in the "on” condition over a period of time, even after the battery had, to the user, gone “flat”.
  • the Low Drain Continuous Test simulates the conditions experienced by a battery in, for example, a clock.
  • HDCT results are measured in terms of the amount of leakage
  • LDCT results are measured in terms of failure of the battery due to perforation or splitting of the can.
  • the Low Drain Continuous Test for an electrochemical cell is characterised in that the can is sealed but left uncovered, a high resistance is secured between the poles of the cell so as to complete a circuit, and the cell is monitored as to its condition.
  • monitoring the cell is intended to ascertain whether the cell fails during testing.
  • the typical lifetime of a D-size zinc carbon cell is up to about 10 weeks when the resistance is about 300 ⁇ . Other resistances may be used as appropriate, although 300 ⁇ provides useful results.
  • -An appropriate resistance for a C-size cell is about 500 ⁇ while, for an AA-size cell it is about 810 ⁇ .
  • the omission of the bottom cover and the over tube is to expose the can to a surrounding atmosphere, thereby enhancing any failure that might occur, which is one reason why this test can be performed in 10 weeks, when it might take 2 years in a clock, for example.
  • the High Drain Continuous Test for an electrochemical cell is characterised by the cell being preferably fitted with a bottom cover, a low resistance being secured between the top cover and a point on the can wall proximal to the top cover and, thereafter, sliding an over-tube onto the can so as to cover substantially as much of the can as possible without dislodging the resistance, weighing the resulting assembly, storing the cell at ambient temperature, preferably 20°C, weighing the cell at intervals during storage if desired, and determining the amount of electrolyte lost during storage by weighing to establish leakage.
  • This last weighing may be effected by removing and weighing the over tube after storage or weighing the cell without the over tube but with the resistance, or both. Addition of the bottom cover during this test is particularly advantageous in preventing corrosion at the bottom of the can during the test .
  • a suitable resistance for this test for a D-size cell is 3.9 ⁇ and about 5 ⁇ for an AA-size cell, and the test is typically carried out for 4 weeks, testing at weekly intervals.
  • the normal discharge life for a D cell is about 6 hours in this test until the cell becomes useless.
  • Testing for 4 weeks for example, establishes how the cell stands up to abuse conditions.
  • the present invention will now be illustrated with respect to the accompanying, non-limiting Examples wherein percentages are by weight, unless otherwise specified.
  • the Test Examples are preceded by certain Test Protocols appropriate to the Test Examples.
  • the zinc cans used in the present examples typically comprise 0.4% lead and 0.03% manganese and have a wall thickness of 0.46 + 0.03mm.
  • the mix for the cathode typically comprises 52% manganese dioxide, 0.4% zinc oxide, 6% acetylene black and 41.6% zinc chloride solution (26.5% zinc chloride w/v) . Otherwise, cells are generally manufactured in accordance with EP-A-303737.
  • the first step in the preparation of a separator is to prepare the paste to be used for the coating of the paper.
  • the formulations used in the present Examples were as follows :
  • Suitable additives are commonly available as surfactants, typically as provided in "Industrial Surfactants Electronic Handbook” (published by Gower and edited by Michael and Irene Ash) .
  • the following method was employed for making up the paste: mix the dry ingredients then add to the water and organic additive and place the resulting mixture in a paddle mixer, such as a Hobart mixer, and mix until a smooth paste is obtained.
  • the separator paste is then coated onto the chosen paper.
  • the technique used in the Examples is to run the coated paper between two rollers set apart by a predetermined distance in order to provide the desired coating weight when dry.
  • the rollers are suitably set so that they run in opposite directions, with the forward roller running fastest.
  • a suitable coating machine is made by Dixon's (Dixon's Pilot Coating Machine Model 160, UK).
  • Suitable coating weights will be apparent to those skilled in the art. However, we prefer a dry coating weight of around 40gm " .
  • the coated paper is then dried either by oven-drying at 100-140°C and/or by steam drum-drying at 100-150°C.
  • Cell is manufactured as above. The bottom cover is added but no over-tube.
  • resistors are soldered between the cover and the top of the can adjacent the cover. Cells are weighed (w x ) .
  • Over-tubes are weighed (w 2 ) .
  • the over-tube is pushed on cell but not spun in.
  • the cell is weighed (w 3 ) .
  • the HDCT cells are stored at 20°C for 4weeks .
  • the normal discharge life for D cells on a 3.9 ⁇ test is ⁇ 6h.
  • This test for 4w represents an abuse test to simulate a consumer leaving equipment switched on.
  • the over-tube is removed and weighed (w 5 ) .
  • the HDCT leakage is W x - W 6 .
  • LDCT Low Drain Continuous Test
  • Cell is manufactured as above. For LDCT no bottom cover is added and no over-tube.
  • 300 ⁇ resistors are soldered between the cover and the top of the can adjacent the cover.
  • Cells are monitored at weekly intervals up to lOw. This would be the normal lifetime for a D cell on a 300 ⁇ test. This test is a simulation of a cell being used on a long duration test such as a clock.
  • a failure is when perforation or splitting of the can is observed. This would allow 0 2 into the cell causing premature failure when on a long duration test .
  • LIF Light Industrial Flashlight
  • Toy (also referred to as DT herein) - similar to motor, except that cells are discharged across a resistance of 2.2 ⁇ for l hour a day until the failure voltage of 0.8V is reached. The final result is the cumulative total of discharge time prior to failure of the cell.
  • Continuous Toy (also referred to as DY herein) - cells are discharged continuously across a resistance of 2.2 ⁇ until cell failure at 0.75V.
  • the final result is the cumulative total of discharge time prior to failure of the cell.
  • DP - cells discharged across a resistance of 2.2 ⁇ for 8 periods of 4 minutes in one hour, each period separated by about 2 minutes. This is repeated daily and the final result is given in terms of hours, being the cumulative total of four minute discharge periods undergone until the failure voltage of 0.9V is reached.
  • the mix used in the following Examples was 2.35 g H 2 0/Ah, 0.34% (w/w) ZnCl 2 /H 2 0, with 50% PRC Mn0 2 and 50% N65 Mn0 2 , unless otherwise specified.
  • potato starches are:
  • ES cells were made up with the following separators and tested in the SCA and HDCT tests v ES cells PI indicates the relative performa of the cells against ES cells
  • EO indicates the oxyethylene content of the additive
  • Crodamet C5 Coconut 5 12 61 96% 12 - - -
  • Potato starches are relatively coarse (average particle size 0 04-0 06mm), while wheat (average particle size 0 006-0 015mm) & corn (average particle size 0 006-0 017mm) are relatively fine
  • AW pulse - cell is discharged for 15 seconds every minute across 1 8 ⁇ until failure at
  • the optimum coating weight for potato starch is apparently 40gsm, serving to maximise performance & minimise HDCT leakage
  • various different papers are tested in accordance with the invention. The tests are performed with tallow 8 but, even so, it is clear that all papers coated in accordance with the present invention confer superior characteristics on the cell containing them.
  • the starch was Roquette LAB 2273, the gellant was Courtaulds 1209, the adhesive was ISP PVP K120 and the additive was Tallow 8 amine.
  • Table 14 illustrates how the results of the JIS test were scored The total for each batch of 20 forms the leakage index

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Abstract

Séparateurs pour cellules électochimiques dont l'enduit est notamment composé d'un amidon cationique, permettant aux cellules d'obtenir de meilleurs résultats dans les essais portant sur la capacité de stockage et la performance.
PCT/GB1997/002148 1996-08-09 1997-08-08 Separateurs en papier couche pour cellules electrolytiques Ceased WO1998007204A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU38577/97A AU723792B2 (en) 1996-08-09 1997-08-08 Coated paper separators for electrolytic cells
EP97935681A EP0947017A1 (fr) 1996-08-09 1997-08-08 Separateurs en papier couche pour cellules electrolytiques

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB9616703.6 1996-08-09
GBGB9616703.6A GB9616703D0 (en) 1996-08-09 1996-08-09 Improved electrolytic cells and components therefor
GBGB9625325.7A GB9625325D0 (en) 1996-12-05 1996-12-05 Improved electrolytic cells and components therefor
GB9625325.7 1996-12-05
GBGB9711646.1A GB9711646D0 (en) 1997-06-05 1997-06-05 Improved electrolytic cells and components therefor
GB9711646.1 1997-06-05

Publications (1)

Publication Number Publication Date
WO1998007204A1 true WO1998007204A1 (fr) 1998-02-19

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PCT/GB1997/002148 Ceased WO1998007204A1 (fr) 1996-08-09 1997-08-08 Separateurs en papier couche pour cellules electrolytiques

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EP (1) EP0947017A1 (fr)
KR (1) KR20000029983A (fr)
CN (1) CN1234138A (fr)
AU (1) AU723792B2 (fr)
WO (1) WO1998007204A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999035700A3 (fr) * 1998-01-02 1999-12-02 Ever Ready Ltd Separateurs pour piles au carbone de zinc
EP2276092A1 (fr) 2002-02-12 2011-01-19 Eveready Battery Company, Inc. Pile a couche mince flexible a electrolyte gel et procedure pour sa fabrication

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102382196B (zh) * 2011-08-24 2013-07-10 广西大学 一种阳离子纤维素的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57202657A (en) * 1981-06-08 1982-12-11 Matsushita Electric Ind Co Ltd Alkaline battery
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WO1999035700A3 (fr) * 1998-01-02 1999-12-02 Ever Ready Ltd Separateurs pour piles au carbone de zinc
EP2276092A1 (fr) 2002-02-12 2011-01-19 Eveready Battery Company, Inc. Pile a couche mince flexible a electrolyte gel et procedure pour sa fabrication

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AU723792B2 (en) 2000-09-07
CN1234138A (zh) 1999-11-03
KR20000029983A (ko) 2000-05-25
AU3857797A (en) 1998-03-06

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