CN1234138A - Coated paper separators for electrolytic cells - Google Patents

Abstract

Separators for electrochemical cells having a cationic starch as a component of their coating allow the cells to perform better in storage and performance tests.

Description

The coated paper separators for electrolytic of battery

The present invention relates to the electrochemical cell of coated paper separators for electrolytic, wherein separator plate coating contains starch and additive, the invention still further relates to such dividing plate.

Under the pressure of the safety of improving dry cell (being also referred to as zinc carbon or carbon zinc battery here) and performance characteristic, people have studied the various components as the battery mixture of manganese dioxide and so on, in order to compensate the use amount that reduces mercury, have also added various additives.What the past did not also study in great detail is dividing plate or separator plate coating.This mainly is because the sole purpose of initial cognitive use dividing plate is to prevent from directly to electrically contact between two electrodes, allows the ion contact simultaneously.

Astoundingly, we have confirmed that dividing plate and separator plate coating can influence the performance and the security feature of battery very significantly, its influence degree even in the SCA of novelty (short circuit current intensity) test battery is improved.

Treating altogether among the trial application PCT/GB96/01318 as this paper list of references, we have described by as the high crosslinked starch of Vulca 90 (trade mark of National) and so on and the advantage of making separator plate coating as the gelling agent of CELACOLB1209 (trade mark of Courtauld) and so on, and these materials can not decompose in liquor zinci chloridi when storing.In addition, as the treating altogether among the trial application PCT/GB96/01319 of this paper list of references, we have also confirmed to add and have contained the polyoxyalkylene nitrogen compound or be good as the additive of Crodamet C20 and so on.Crodamet C20 is the monoamine that contains two polyoxyethylene side chains, and every mole of Crodamet C20 on average has 20 mole oxygen ethylene unit.

In many standard cell tests, contain the dividing plate of the coating of said components, make the dry cell performance that obtains obviously more much better than the dry cell that contains standard ingredient.Especially true under the condition of improper use.Test under many improper service conditions is arranged, but we design two tests, checked the leakage situation (HDCT and LDCT test are described later on) under non-normal condition.The HDCT experimental examination in a period of time, be under " opening " situation when photoflash lamp, even " use up " those situations that may run into afterwards at battery for the user.The LDCT test simulation one batteries situation about in clock for example, taking place.The advantage of these tests is that these tests can carry out quite soon, needn't wait for and determine just about 1 year that whether battery can work and do not leak in clock for example.

In treat trial application PCT/GB96/02739 altogether as another of this paper list of references, the character that we also find to be used for the paper of dividing plate has very big influence, and it is all better than any paper that uses in standard cell at present again to absorb at least 4 minutes high-density paper of 50 microlitre water droplets flower.

Although described carbon zinc battery dividing plate still has shortcoming generally successfully doing various improvement aspect the leakage that reduces basically under the non-normal condition, the battery performance that Here it is contains such additive descends a little.Thereby the improvement that we do dividing plate makes battery leak possibility under non-normal condition to reduce greatly, and this itself is exactly very desirable, and is the main target in the battery production.But, to compare with the battery of this technology, its downward trend is that these batteries also have the life-span of more or less reducing, the relation between therefore necessary balance minimum leakage desirability and the reduction possibility in useful life.

Astoundingly, we have now found that, if use cationic starch in the production of the separator plate coating of battery, the storage that the battery of such dividing plate is housed so has very large raising, even battery also can be worked finely after storing under the strictest condition.In addition, we found to make with equal performance of the battery of present technique or the better battery of performance be possible, battery is loaded onto the coated paper separators for electrolytic that not only contains cationic starch but also have low hydrophile-lipophile balance (HLB) additive, just can accomplish this point.

Thereby, the first, the invention provides a kind of coated paper separators for electrolytic of electrochemical cell, this coating contains starch, it is characterized in that cationic starch has constituted the major part of the starch ingredients in the separator plate coating.

On the other hand, the invention provides a kind of coated paper separators for electrolytic that is used for electrochemical cell, this coating contains starch and additive, it is characterized in that starch is cationic starch, and the hydrophile-lipophile balance of additive is lower than 17.

In the past, we had determined that a particularly advantageous class additive is the additive that can be categorized as surfactant usually, especially preferably contained the polyoxyalkylene nitrogen compound.We also determine in the past, wish that especially starch wants high crosslinked, and high crosslinked starch and the best combination of additive are as the starch of Vulca 90 and so on as the polyoxyethylene amine of Crodamet C20 and so on.20 oxygen ethylene unit are on average arranged in each amine among the Crodamet C20, and 12 carbon atoms of on average having an appointment of the alkyl on its amine.The HLB of Crodamet C20 is 17.

Obviously improved the storage of battery although find cationic starch, still had problems under light industry photoflash lamp (LIF) test, in some cases, performance is still than this technology battery low about 10.In the past, the experiment of carrying out with the additive that hangs down the HLB value had improved the result that the LIF test obtains a little, worsened more seriously but make to leak.Astoundingly and cationic starch when using together, we find not only to have improved performance with HLB basically less than 17 additive, and or even HLB be low to moderate 5 o'clock, it is insignificant that leakage problem also becomes.

In the test of following, under the situation of test, we find that cationic starch and Crodamet C20 are used in combination the result who obtains, and under the LIF test, only are 88% of this technology battery.As mentioned above, the HLB of Crodamet C20 is 17, and it is higher than the HLB of requirement of the present invention.

Bound by theory not, we think that the present invention uses the hydrophilic relatively cationic property of starch to allow to use the additive with low HLB of hydrophilic relatively (or lipophilic).

We find that the relative hydrophily of non-cationic starch represents that zinc/dividing plate boundary zone tends to parching in the performance test (as LIF) for a long time, and the power consumption height is all the more so if especially lack discharge time.LIF is exactly the short good example that matches with power consumption height discharge time.Parching during this test can cause increasing at zinc/baffle region battery internal resistance, and the result makes the battery premature failure.Owing to venting is worse off this.Why Here it is seals up the reason that battery is done some test with epoxylite.Can combustion gas although many commodity batteries are made under predetermined pressure, some battery still can prevent exhaust effectively because sealing is very tight, is used for imitating such battery so epoxylite seals.Seal at epoxylite and to prevent gas when when discharge overflows, lower discharge performance when it has also caused LIF.Seal up in the following example of LIF test of battery at " no epoxy resinoid " and " epoxylite ", this is very noticeable.

Thereby we have now found that under LIF test, and HLB is 14 additive and the battery of technology in the past plays good effect about the same, and its value is 96% of a prior art battery, and HLB is that 11 additive obtains in fact equal value (99%) in the LIF test.In both cases, the possibility of leakage reduces a lot than prior art.But, it is shocking that in a single day HLB reaches 9 most, the performance of LIF test is just than the battery of prior art more than 10% so.Thereby no matter from which aspect, battery of the present invention has the additive of so low HLB, and its battery is better than the battery of prior art.

From as can be seen above, HLB makes battery less than 17 any additives :-a) at the battery that is better than prior art aspect the leakage possibility that reduces, and b) be better than containing the battery of cationic starch and Crodamet C20 combination.

Therefore, HLB can be used for dividing plate of the present invention less than 17 any additives, but people can find, HLB is that the additive below 14 or 14 is preferred, because these additives have and the essentially identical performance of the battery of prior art battery product, but the possibility that these battery products leak under improper service condition is much smaller.

Particularly preferred additive is HLB less than 11 additive, because in fact these additives can make performance improve, even to compare with the battery of prior art also be like this.We at present preferred HLB is 9, because this value can make and have HLB and be low to moderate 5 additive and have very close LIF performance, but this more or less increase with the additive that so low HLB is arranged is leaked irrelevant.But, it is still much smaller than prior art battery that HLB is low to moderate the possibility that 5 additive leaks under non-normal condition.Thereby the preferable range of HLB is 5-11,7-10 especially, and 8 or 9, particularly 9 is very preferred.

The HLB of additive is by as the hydrophobic ingredient of alkyl chain and so on as due to the balance between the hydrophilic component of oxygen ethylene unit and so on.In Crodamet C20, mean alkyl chain length is 12, and the average of oxygen ethylene unit is 20, and in fact corresponding with the amine that replaces two decameric polyoxyethylene unit, this amine is also replaced by the C12 alkyl side chain in addition.But people can be appreciated that chemical compound lot can be mixed with the product that belongs to together that is referred to as Crodamet C20.

In order to reduce HLB, can reduce oxygen ethylene unit number, increase alkyl side chain length.Crodamet C20 is that 12 coconut alkyl group is a main component with aforesaid average chain length mainly.The HLB that contains the Crodamet T5 of five oxyethylene group groups is 12.Therefore, require to increase mean alkyl chain length usually, so we have found that tallow provides useful alkyl length, average about 18 carbon atoms.Ethylan TT203 is the amine that the alkyl of two oxygen ethene substituting groups and 18 carbon atoms of an average length is arranged, and its HLB is 5.For HLB is 9, and Crodamet T5 (5 oxyethylene group groups are arranged) is preferred.However, it should be understood that in order to obtain having the additive of the HLB that requires, can adopt any suitable method to change alkyl chain length and oxygen ethylene unit number.

In addition, for the additive with low relatively HLB, preferably these additives should be nonionics, and for the present invention, nonionic additives is preferred.

As used herein, term " cationic starch " relates in its molecular structure, and each starch molecule on average contains at least one cationic any starch on the spot.

Cationic starch is known in this technical field, and for example at " starch, chemistry and technology (Starch; Chemistry and Technology) " (Academic Press, Inc., Eds.Whistler, R., Bemiller, J., and Paschalle, E., open second edition in 1984).Usually, can prepare cationic starch, list in this paper with list of references as GB-A-2063282 and US-A-4613407 disclosed method.

US-A-4613407 has described cereal and the stem tuber cationic starch cooperates the green end cationic additive that is used as paper production.These two pieces of lists of references have usually proposed the application of many kinds of cationic starches, but do not think in the past that cationic starch can be used for electrochemical cell.

As described in GB-A-2063282, can be by common starch be dissolved in water, and under the highly basic condition, allow described starch and suitable cation-exchanger contact preparation cationic starch.The reagent that illustrates among the GB-A-2063282 is low alkyl group halohydrin and low alkyl group halogenated epoxide, and being suitable for production viscosity, these compounds are higher than 1000, even the cationic starch of 2000 Brabender units (in water with 5% (w/w) concentration determination).

As described in the prior art, usually preferred nitrogen content level is with starch dry weight basis 0.2-2% (w/w), although this content rises to 2.8%.Be the real upper limit be by the chemistry and the actual limit of cost reason defined.

Usually, we feel preferable is basically as prepare separator plate coating by method known in the art, but adds cationic starch, replaces some or all starch ingredients in the coating.Preferred paper and other components are generally as described herein.

Cationic starch should constitute the major part of starch ingredients in the separator plate coating, and usually, we feel preferable is that it constitutes whole starch ingredients, although need to add other components sometimes, for example Vulca 90.

Usually, to the character of cationic starch of the present invention without limits.But, often may require the cationic starch should be not water-soluble rapidly, in this case we would rather it and not exclusively water-soluble (being cold water at least) and it in the presence of water, do not expand.But cationic starch should be partial cross-linked at least.The effect of uncrosslinked cationic starch and unsatisfactory is although seem not have a lot of difference between the two the performance of high crosslinked starch and medium crosslinked starch.

Starch can be any suitable starch.Known have many suitable starch, comprises potato, corn, wheat and tapioca.Cationic character also is unessential, although because environment reason, preferably this material is nontoxic usually.

Suitable cation is Liu, Phosphonium and ammonium ion, and wherein ammonium ion is preferred, they can be added in the starch as suitable alkylation molecule.Under the acid condition of zinc-carbon cell, suitable alkylamine is easy to produce the starch that is replaced by the trialkyl ammonium group.

If used cationic starch is for example starch form of dialkyl amido replacement, just this precursor product can be changed into the cation product with acid by suitable processing so, this conversion can be carried out in the original place, also can carry out before dividing plate is added battery.

Particularly preferred cationic starch of the present invention be No. 2273, LAB by Roquette (Roquette Fr*res, 4 rue Patou, F-59022 Lille C*dex, France) farina of producing, but other producers also make the cationic starch of suitable grade.

Production median septum at dividing plate need use gelling agent usually.As if various soluble starch gelling agents and natural gum that we have found to be used for to produce dividing plate can both decompose at storage process.But the cellulose derivative of etherificate likes stable in solder(ing)acid well, and they are particularly advantageous for the present invention.Being used for suitable gelling agent example of the present invention comprises: Tylose MH200K (trade mark of Hoechst), Tylose MH50, CulminalMHPC100 (trade mark of Aqualon) and Courtaulds DP 1209.

Particularly preferred etherified cellulose derivative ideally should swelling, basically form colloid at once, and in the presence of water, can keep stable in long-time, cellulose derivative as describing among the PCT/GB96/01318, suitable etherified cellulose comprises methylcellulose, ethyl cellulose, CMC, carboxymethyl cellulose (comprising salt, as sodium salt), hydroxyethylcellulose, ethylhydroxyethylcellulose, methyl hydroxyethylcellulose, 2-hydroxypropyl cellulose, methylhydroxypropylcellulose and 2-hydroxypropyl methylcellulose.

We have determined that viscosity is to select a key factor of gelling agent.If the dividing plate mixture outside certain range of viscosities, usually the 3000-70000 centipoise (the 3-70 handkerchief. second) in the scope, can not get closing result and the measured battery of matter that needs usually.For example, 3000 centipoises (3 handkerchiefs. second) below, the liquid that mixture is normally such, it directly is drawn onto in the paper, this can cause for example breaking of paper.70000 centipoises (70 handkerchiefs. second) more than, mixture is too thick usually, so that launch on paper unsatisfactorily.

Therefore, be desirable to provide a kind of mixture in above-mentioned scope, by use about 20 centipoises of viscosity (0.02 handkerchief. second)-300 centipoises (and 0.3 handkerchief. second) the etherified cellulose derivative, it is normally possible to obtain this mixture.(unless otherwise indicated) as used herein, material viscosity are according to the aqueous solution definition of 2% (weight per volume) this material under 20 ℃, neutral pH.This viscosity be ideally the 50-100 centipoise (the 0.05-0.1 handkerchief. second).

Additive used according to the invention is the nitrogen-containing compound of any kind suitably, and it is suitable for being replaced by one or more polyoxyalkylenes.Although amine and ammonium compounds are preferred, amines especially, it also is suitable containing other compounds that can replace the nitrogen key, as carbamoyl, diazo and aci-nitro compound.

Single alkylene moiety can be identical or different in the polyoxyalkylene substituting group, but because the production method that such compound uses, they are normally identical.Available alkylidene group often is confined to ethylidene and propylidene group, but is preventing that propylidene group is good not as the ethylidene group aspect the gasification, and it is preferred therefore containing the polyoxyethylene nitrogen compound, particularly polyoxyethylene amine.People will recognize that the low-grade alkylidene mixed group that any certain polyoxyalkylene partly contains just like methyl, ethyl and propyl group and so on all is possible.If this is the case, we think that the average length of alkylidene is two carbon atoms or more desirable near two carbon atoms.

As for nitrogen-atoms, particularly preferably be it and replaced by at least one polyalkylene oxide groups and a saturated or undersaturated alkyl.This group preferred alkyl or alkenyl.Adopt alkenyl usually without any benefit, although also their are imagined interior.Group can be a straight or branched, can be replaced by one or more substituting groups as hydroxyl and halogen atom and so on, but usually preferably alkyl be not substituted.Saturation is saturated fully ideally, perhaps has only the two keys of one or two carbon atom.If the HLB of compound is less than 17, straight chain and the alkyl that contains 1-30 carbon atom also are preferred so.

Compound of the present invention also can contain the amine center more than 1, in this case, preferably uses alkylidene group, preferably as the single amine groups of short chain alkylidene group bridging of trimethylene and so on.

When one or more nitrogen-atoms by a undersaturated group, specifically be alkenyl when replacing, the invention provides the dividing plate that contains such compound that with good grounds PCT GB96 01319 (listing in this paper as a reference) illustrates.In such dividing plate, wherein alkyl chain PCT GB open in 01319, if at least one alkyl is replaced by a undersaturated chain, a so available unsaturated chain replaces this alkyl chain.

For the present invention, if HLB less than 17, the polyoxyalkylene chain length is not a particular importance so, but we think that chain length should be 1-5, preferred average length is 1-3, about particularly 2 or 3 is more desirable.In addition, the compound that is obtained by tallow amine is preferred, and the tallow alkyl contains 18 carbon atoms of having an appointment.

Thereby, most preferred of the present invention is monoamine and diamines, free alkyl 18 carbon atoms of having an appointment wherein, and side chain is the polyoxyethylene substituting group that respectively contains average 1 or 2 oxygen ethylene unit, if compound is a diamines, the connection between two amine centers is a trimethylene so.

Be used to preferred compounds of the invention are the compound that is obtained by tallow now, compare with coconut, it has following composition, and wherein chain length is the carbon atom number:

Chain length	Degree of unsaturation	The acid name	Tallow	Coconut oil
					＜8	?0			1％
8	?0	Sad		5％
					10	?0	Capric acid		8％
12	?0	Laurate		45％
					14	?0	Myristic acid	6％	18％
16	?0	Palmitic acid	27％	11％
					16	?1	Palmitoleic acid		1％
18	?0	Stearic acid	14％	2％
					18	?1	Oleic acid	50％	8％
18	?2	Linoleic acid	3％	1％

Can use any suitable paper according to the present invention, this represents that any paper all is suitable for use as dividing plate.But the most of paper that use in common dividing plate all are by the pulp production of single source, and when producing these paper with cheap relatively cost, many tests of these paper are often bad.Yet we are definite, and it is possible being gone out to show in test good paper by the pulp production of single source, and such paper is characterised in that they can absorb 50 microlitre water droplets in 4-15 minute when about 20 ℃ of temperature.More preferably, this time is 5-15 minute, particularly preferably is 5-10 minute.

If paper has absorbed water droplet being less than in time of 4 minutes, the density of paper is often too low so, may obtain relatively poor result.If paper has absorbed water droplet in greater than 15 minutes time, this can bring practical problem to production so, because single battery need carry out voltage test at once after assembling, from mixture, postpone during absorbed electrolyte to show that a unacceptable storage time is arranged before test cell.

High often making beating of feature and high density feature with paper of necessary absorbability.Before forming paper, paper pulp is pulled an oar, and available " canadian standard freeness verifier (Canadian standard freeness tester) " measures the degree of making beating.This test is the T 227m-58 of paper and pulp industry technological associations (the Technical Association of the Paperand Pulp Industry), and for example at " paper pulp and paper production laboratory manual (A Laboratory Handbook of Pulp and Paper Manufacture) " (author J.Grant, the Edward Arnold of publisher, 1961 the 2nd edition, the 154th page, following) in did the description.

Traditional paper, as Enso 80, its density is about 0.5 gram/cubic centimetre usually, even the density of PBDE100 also only has 0.62 gram/cubic centimetre.But these two kinds of paper all can use according to the present invention, although more highdensity paper is preferred.

The density of the paper of the preferred single sources of paper pulp of the present invention is usually more than 0.64 gram/cubic centimetre reaches, and preferred density is about 0.65-1 gram/cubic centimetre, more preferably density is about 0.65-0.9 gram/cubic centimetre, although the choice is very little in this special density range.For example, the particularly preferred paper of a kind of the present invention is produced (product code COK～70) by Cordier, its density is 0.64 gram/cubic centimetre, and the another kind of particularly preferred paper of the present invention is produced (product code 114440), its density 0.76 gram/cubic centimetre by Munksjo.

The table of the preferred paper of Shi Yonging is as follows in the present invention:

Cordier????????????COK～60

Cordier????????????COK～70

Sibille Dalle 58060 (being called " SDMF " later on)

Munksjo????????????114440

Munksjo????????????114770

Tervakoski?Oy??????Tertrans?N75?0,75

Tervakoski?Oy??????Terkab?E70?10

Can obtain Cordier paper from the Papierfabrik Cordier limited company of German Fa Erci; Can obtain SibilleDalle paper from the Sibille Dalle of French Vitry sur Seine; Can obtain Munksjo paper from the Munksjo Paper AB of Sweden Jonkpong; Can be from Finland Tervakoski, Oy obtains Tervakosko paper.

Density is often relatively poor less than the result that the paper of about 0.6 gram/cubic centimetre obtains in test, and the paper that density surpasses about 1.0 gram/cubic centimetres in the water droplet absorption test absorbent time often more than 15 minutes.

Usually, adopt the battery of the dividing plate that has cationic starch under disadvantageous condition of storage, still to work.In a test, 45 ℃ of temperature in addition after 26 weeks failure rate be 0%.Though do not want to be bound by theory, this extraordinary result looks like because the interface between dividing plate and the container keeps moist.Dividing plate of the present invention has strengthened this effect.Though the total moisture content of battery is basic identical, other dividing plates of this technology are easy to parch.This is the problem with regard to recognizing before, but this problem still is not resolved up to now.

Another advantage of using cationic starch is that the quality of manganese dioxide is unlike in other batteries and constitutes in things important like that.This is a main advantage, because manganese dioxide is mainly expending in the dry cell production, if for example can use relatively cheap electrolytic manganese dioxide (EMD) raw material, just can reduce expenses in a large number.At present,,, could use such low grade material if be used in combination with high-grade material for fear of leakage, if but cationic starch used according to the invention, this is just unnecessary.The present invention uses more cheap material now, for example from the material of the People's Republic of China (PRC), becomes possibility.

Should be appreciated that the present invention also provides the electrochemical cell that comprises dividing plate of the present invention.The coating compound that is suitable for production coating dividing plate of the present invention also is provided, and described mixture contains cationic starch.

Can use the representative cells of dividing plate of the present invention to comprise zinc carbon primary cell and storage battery, be referred to as zinc-carbon cell and the zinc chloride battery of Leclanch* comprising those, and alkaline battery.Electrolyte in the zinc-carbon cell is as follows usually: Leclanch* electrolyte-5-20% zinc chloride, 30-40% ammonium chloride, and all the other are water; Zinc chloride electrolyte-15-35% zinc chloride, 0-10% ammonium chloride, all the other are water.The battery that some other the present invention is suitable for has been described in battery and fuel cell handbook (the Handbook of Batteriesand Fuel Cells) (edited by Dayid Linden, McGraw Hill publishes) the 5th chapter.

Battery can have suitable profile, as circle, square or flat profile.

Here can be used for determining that two useful tests of leaking are high power consumption long run test (HDCT) and low power consumption long run test (LDCT) under non-normal condition.High power consumption long run test is used to simulate non-normal condition, be in a period of time under " opening " situation as photoflash lamp, even " use up " for the user at battery afterwards can detectable situation.The low power consumption long run test has been simulated the situation of battery in clock for example.With the quantitative determination HDCT result of leaking, and with because the battery failure that battery case perforation or break causes is measured the result of LDCT.These tests have obtained providing the result of more information in the time than the following elapsed time much shorter of wanting of the condition that simulated.For example, in about 4 and 10 weeks, obtain the result respectively usually, will depend on as treating test cell and allowing battery test the factors such as degree that will reach although people can be appreciated that the time length that needs.

The low power consumption long run test of electrochemical cell be characterised in that battery case be sealing but block guarantees to have high impedance between the electrode of battery so that constitute a circuit, and check the situation of battery.

Should be appreciated that in this test, check that battery is in order to determine whether battery lost efficacy in test.When resistance was about 300 ohm, the typical life of D zinc-carbon cell was up to about 10 weeks.Though 300 ohm provide useful results, also can suitably use other resistance.The suitable resistance of C battery is about 500 ohm, and the suitable resistance of AA battery is about 810 ohm.Therefore do not have bottom and outer tube to make shell be exposed to surrounding air, increased the possibility that failure conditions takes place, this is why may work 2 years the time reason that this test but can be finished when battery in clock in 10 weeks.

The high flow rate long run test of electrochemical cell is characterised in that, preferably gives battery fit on bottom, guarantee top cover and near on the shell wall of top cover a bit between low resistance is arranged, afterwards, the outer tube that slides on shell with cover housing as much as possible basically, and does not reduce resistance, the assembly of weighing and obtaining, in room temperature, preferred 20 ℃ of storage batteries are if desired at the lay up period battery of weighing at certain intervals, and by the electrolytical loss amount of mensuration lay up period of weighing, to determine leakage.Can take out after storage and the outer tube of weighing is weighed for the last time, or weigh and do not have outer tube but have the battery of resistance to weigh for the last time, perhaps these two kinds of methods can.Add that in this process of the test bottom is particularly advantageous to the bottom corrosion that prevents the process of the test mesochite.

The suitable resistance of this D type battery testing is 3.9 ohm, AA type battery be 5 ohm, carry out this usually and tested for 4 weeks, test in weekly gap.In this test, the regular picture time limit of D type battery is about 6 hours, can not use up to battery.For example, tested for 4 weeks to determine how battery bears improper service condition.

Also will the present invention be described with non-limiting example below, wherein unless otherwise indicated, percentage is percetage by weight.Before experimental example be and corresponding some testing program of experimental example.Unless otherwise indicated, the cadmia that uses in the present embodiment contains 0.4% plumbous and 0.03% manganese, 0.46 ± 0.03 millimeter of wall thickness usually.Cathode mix contains 52% manganese dioxide, 0.4% zinc oxide, 6% acetylene black and 41.6% liquor zinci chloridi (26.5% zinc chloride (weight per volume)) usually.In addition, battery is produced according to EP-A-303737 usually.

Testing program

The preparation of dividing plate

The first step of preparation dividing plate is the pastel that preparation is used to be coated with paper.The prescription that present embodiment uses is as follows:

Water 64.3%

Additive 0.5%

Gelling agent (as regulation) 3.1%

Starch (Vulca 90 normally unless otherwise indicated,

Or Roquette 2273) 32.1%

Suitable additive normally obtains with surfactant, typically as the surfactant of " industrial surface activity agent electronic documentation (Industrial Surfactants E1ectronic Handbook) " (publish by Gower, edit) defined by Michael and Irene Ash.

Adopt following method to prepare pastel: the component of mix doing, add to then in water and the organic additive, the mixture that obtains is put in the paddle mixer as Hobart mixer and so on, mix then up to the pastel that obtains mixing well.

Then the dividing plate pastel is coated onto on the selected paper.The technology of Shi Yonging is in order to obtain desired coating weight when the drying in an embodiment, passes through coating paper between two rollers of preset distance separately.This two rollers suitably are set, they are rotated with opposite direction, roller forward changes the most soon.Suitable coating machine is made by Dixon ' s (Dixon ' s PilotCoating Machine Model 160, Britain).

Those skilled in the art know suitable coating compounds weight very much.But we feel about 40gm ^-2Dry coating weight is more desirable.

Use the oven drying coating paper at 100-140 ℃ then, and/or at 100-150 ℃ with the drying coated paper of steam drum.

Acquiescence battery among the embodiment has following composition, and ES represents the battery in present technique field:

	ES	Test cell
			Starch	90.9％????Roquette Vector?L117	?87.9％????Roquette ?LAB2273
?N *	0％	?0.2％
			Crosslinked	Medium	Medium
Gelling agent	8.7％Tylose?MH200K	?8.4％?Courtaulds?1209
			Adhesive	??-	?2.2％?ISP?PVP?K120
Additive	0.4％Forofac?1110D	1.5% low HLB additive
			Paper	Sibille?Dalle?WS64	?Munksjo ?14440(M114440)
gsm *	50	?40
			The gel mixed method	Wet method	Dry method
Final drying means	Baking oven	Steam drum (the 1st baking oven)

N ^*: the nitrogen content of cationic starch (% w/w)

Gsm ^*: drying composite gram number on every square of rice paper

Unless otherwise indicated, every other battery is all prepared by the dry mixed gel component, and gsm is 40.Final drying is by the steam drum drying.We have found to use as the adhesive of polyvinylpyrrolidone (PVP) and so on and have gone far towards coating with the steam drum drying and have been attached on the paper.We also determine, when starch was farina, best gsm was about 40, and we think that this is effectively corresponding to the individual particle layer on paper.Wheat or cornstarch are better, only need be coated with about 20gsm, although its amount is strict unlike farina.

HDCT (high flow rate long run test)

1, makes battery as mentioned above.Add bottom but do not add outer tube.

2, between the top of lid and the contiguous shell that covers, link 3.9 ohmic resistors.Battery (W weighs ₁).

3, the outer tube (W that weighs ₂).

4, outer tube is pushed away on battery, but not precession is gone.Battery (W weighs ₃).

5, store HDCT 4 weeks of battery at 20 ℃.3.9 when test ohm, the regular picture time limit of D type battery is～6 hours.This test that continued for 4 weeks has showed analog subscriber makes facility switching be in the non-normal condition test of open position.

6, week about (1w, 2w, 3w and 4w) removes 1/4 original battery and measures.Battery (the W of discharge fully weighs ₄).

7, remove the outer tube and the (W that weighs ₅).

8, the still undamaged battery (W that has the connection resistance device that weighs and obtain ₆).

9, the HDCT leakage is W ₁-W ₆

LDCT (low consumption is by long run test)

1, produces battery as mentioned above.The LDCT test does not add bottom, does not add any outer tube.

2, between the top of lid and the contiguous shell that covers, connect 300 ohmic resistors.

3, monitor primary cell week about, up to 10 weeks.Ordinary life when this should be 300 ohm of tests of D type battery.This test simulation the battery that uses of long term test, as the battery in the clock and watch.

4, when boring a hole or break, shell observed battery failure.This may be to allow O when testing for a long time ₂Enter battery and cause its battery premature failure.

In following examples, various industrial standard tests have been carried out.Unless otherwise indicated, the battery of test is the D battery.Under unqualified situation, these tests are as described below:

SCA-makes battery short circuit, measures the electric current that passes through with zero impedance meter (very low).The measured value that obtains is SCA (short circuit current intensity) value of this battery.

LIF (light industry photoflash lamp)-battery discharged 4 cycles by 2.2 Ohmic resistances in 1 hour, 8 minutes each cycles, about 2 minutes of each all period interval.Repeat this process every day, final result is hour to provide, and the result is through 8 minutes discharge cycle cumulative totals when reaching 0.9 volt of inefficacy voltage.

Make battery discharge 1 hour by 3.9 Ohmic resistances engine (being also referred to as DM here)-every day, up to reaching 0.9 volt of inefficacy voltage.Final result is the cumulative total of discharge time before the battery failure.

Toy (being also referred to as DT here)-similar to engine test is except making battery discharge 1 hour by 2.2 Ohmic resistances every day, up to reaching 0.8 volt of inefficacy voltage.Final result is the cumulative total of discharge time before the battery failure.

Continuous toy (being also referred to as DY here)-make battery discharge by 2.2 Ohmic resistances continuously, up to battery 0.75 volt of inefficacy.Final result is the cumulative total of discharge time before the battery failure.

DP-made 8 cycles of battery discharge by 2.2 Ohmic resistances in 1 hour, 4 minutes each cycles, about 2 minutes of each all period interval.Repeat this process every day, final result in hour, the result is the cumulative total of 4 minutes discharge cycles when reaching 0.9 volt of inefficacy voltage.

Unless otherwise indicated, the mixture that uses in the following example all is 2.35 gram H ₂O/Ah, 0.34% (w/w) ZnCl ₂/ H ₂O and 50%PRC MnO ₂With 50%N65 MnO ₂

In following examples, farina is:

	N content	Crosslinked
			Roquette?LAB2273	?0.2％	Moderate
Roquette｜13-96	?0.7％	Moderate
			Roquette｜14-96	?0.2％	Very high

Battery performance with different polyethylene glycol oxide additives is made battery with following dividing plate, and has carried out SCA and HDCT test with respect to the ES battery.PI shows the battery with respect to ES, the relative performance of these batteries.Item EO represents the content of ethylene oxide in the additive.

Table 1

Starch Vulca 90 Roquette LAB2273

Gelling agent Tylose MH200K Courtaulds 1209

Adhesive does not have ISP PVP K120

The powder that gellant combination is wet

Paper Enso 80 Enso 80

Final drying baking oven steam drum

Mix?H ₂O/Ah?????2.20??????????????????2.35

ZnCl ₂/H ₂O?????0.34??????????????????0.34

Alkyl EO amine

Alkyl EO HLB SC PI HDCT SC PI HDCTES----6.8 100% 2.7 6.3 100% 3.0

EthylanTT40 tallow 40 18 6.8 98% 1.7 7.3 91% 0.6

Crodamet coconut 20 17 6.5 97% 1.1 6.4 96% 0.5

# tallow 15 14 6.4 97% 0.9 7.7 98% 0.8

Crodamet C5 coconut 5 12 6.1 96% 1.2---

Crodamet T8 tallow 8 11---6.6 99% 0.7

* tallow 59 5.7 95% 1.9 6.9 103% 0.6

Ethylan tallow 25 5.3 93% 2.0 6.7 103% 1.0# Crodamet T15, Ethylan TT15* Crodamet T5, Ethylan TT05, Proxonic MT05

As can be seen from the above table, the battery that obtains of cationic starch LAB2273 and tallow 5 combinations has lower leakage possibility (HDCT) and higher new short circuit

Current strength.Another kind of potato cationic starch by Roquette Freres obtains obtains following result as shown in table 2.

Table 2

LIF

The medium Courtaulds1209/ tallow of NO Araldite Araldite cap % HDCT starch N X-Link gel/adhesive alkyl EO paper No.Avg. No. Avg. of ES 9Roquette LAB2273 0.2% 8 M114440 24 7.0 33 6.1 99% 0.7

The medium Courtaulds1209/ tallow of ISP PVP K120Roquette|13-96 0.7% 8 M114440 3 6.5 3 7.2 105% 0.1

The very high Courtaulds1209/ tallow of ISP PVP K120Roquette|14-96 0.2% 8 M114440 3 8.0 3 6.8 112% 0.1

ISP PVP K120 table 2 (continuing) SCA No. DP DM DT DY PI6.6 21 6.9 15.0 8.1 6.3 100% 100% 100% 100% 100%6.9 3 6.5 15.7 8.6 6.3 101%

94％???105％????106％???101％6.9????3????8.0????15.8??????8.8?????6.0????106％

115％???106％????108％????96％

Although carried out this embodiment with tallow 8 (HLB11) rather than tallow 5 (HL8), can see the character of cationic starch

Inessential, condition is if it is appropriately crosslinked at least.In table 3, to have determined to compare with the ES battery, additive character is to Effect on Performance.

Table 3

LIF??????????????????LIF????.

NO?Araldite?Araldite?cap

% starch N X-link gel/adhesive alkyl EO HLB paper No. Avg. No. Avg. of ES

ES 21 7.0 34 6.2 100%Vulca 90 TyloseMH200K coconuts 20 17 PBDE100 6 8.3 6 5.1 86%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ coconut 20 17 Singer 70 15 5.9 33 4.8 81%

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ nothing-M114440 3 5.6 15 4.9 79%

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 40 18 M114440 3 5.1 21 4.9 77%

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ coconut 20 17 M114440 4 6.1 11 5.5 88%

ISP PVP K120 Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 15 14 M114440 3 6.7 10 5.9 96%

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ coconut 5 12 M114440 5 6.6 3 6.0 96%

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 8 11 M114440 24 7.0 33 6.1 99%

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 59 M114440 18 7.4 61 7.2 111%

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 25 M1114440 12 7.7 26 7.1 112%

ISP?PVP?K120

No Aratdite.

Starch N X-link gel/adhesive alkyl EO HLB paper No DP DM DT DY PIES 15 6.7 15.1 8.6 6.3 100%

100％??100％????100％??100％

Vulca 90 Tylose MH200K coconuts 20 17 PBDE100 3 6.4 14.8 8.4 6.5 98%

95% 98% 98% 103%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ coconut 20 17 Singer 70 3 4.7 14.8 8.3 6.4 91%

ISP?PVP?K120

70% 98% 97% 101%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ coconut 20 17 M114440 3 58 15.6 7.9 6.3 95%

ISP?PVP?K120

86% 103% 92% 100%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 40 18 M114440 3 51 14.9 8.5 5.8 91%

ISP?PVP?K120

76% 98% 99% 92%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 15 14 M114440 3 6.7 14.8 8.2 6.2 98%

ISP?PVP?K120

99% 98% 96% 98%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 8 11 M114440 21 6.9 15.0 8.1 6.3 99%

ISP?PVP?K120

103% 99% 95% 99%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 59 M1114440-18 7.4 15.4 8.3 6.6 103%

ISP?PVP?K120

109% 102% 97% 104%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 25 M114440 12 7.7 16.3 8.2 6.1 103%

ISP?PVP?K120

114% 107% 96% 97% have Araldite.

Starch N X-link gel/adhesive alkyl EO HLB paper No DP DM DT DY PIES 6 6.1 14.1 8.1 6.3

100% 100% 100% 100%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 8 11 M114440 9 5.9 15.8 8.3 6.1 102%

ISP?PVP?K120

97% 113% 102% 97%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 59 M114440 9 6.5 16.2 8.2 6.4 107%

ISP?PVP?K120

108% 115% 102% 102%Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 25 M114440 9 6.9 15.6 8.1 6.1 105%

ISP?PVP?K120

113% 111% 100% 96% 105% in table 4, and the effect of additive in the HDCT test is described.The result represents with gram/battery average leaked.

Table 4ES starch N X-link gel/adhesive alkyl EO HLB GSM paper No. Avg.Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 40 18 40 M114440 10 0.6

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ coconut 20 17 40 M114440 10 0.5

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 15 14 40 M114440 10 0.8

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 8 11 40 M114440 10 0.7

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 59 40 M114440 30 0.6

ISP PVP K120Roquette LAB2273 0.2% Mod. Courtaulds 1209/ tallow 25 40 M1114440 10 1.0

ISP?PVP?K120

Can be clear that the additive of all tests all obtains surpassing the good results of prior art battery, even HLB is that 5 additive also is very favourable.

The gram number (gsm) of drying composite on every square metre of coating

Farina is thick (particle mean size 0.04-0.06 millimeter) relatively, and wheaten starch (particle mean size 0.006-0.015 millimeter) is relative thinner with cornstarch (particle mean size 0.006-0.017 millimeter).

This has following influence to AA type battery.

Table 5

Crodamet C20 and Sibille Dalle MF60 paper are used in this test, have contrasted 20 and 40gsm farina (Roquette LAB2273).

gsm	Starch	SCA	The AW pulse	AZ?Cont.
					20	Cationic potato	2.3 peace	122 weeks	1.6 hour
40	Cationic potato	3.0 peace	144 weeks	1.7 hour

AW pulse-made battery discharge 15 seconds by 1.8 Ohmic resistance per minutes is up to 0.9 volt of inefficacy.

AW-makes battery continuous discharge by 3.9 Ohmic resistances, up to 0.75 volt of inefficacy.

The 40gsm potato obviously is better than the 20gsm potato.It is so thick that reason likes the 20gsm farina well, so that can not cover paper fully.

Table 6

This test uses Tallow 8 Amine (Crodamet T8) and Munksj*114440 paper to contrast 40gsm and 50gsm farina (Roquette LAB2273).

????gsm	????HDCT
		????50gsm	1.9 gram
????40gsm	0.6 gram

This table shows that if be coated with the above farina of 40gsm HDCT just begins to increase so.

The best coating weight of farina is 40gsm, and it is minimum that best performance and HDCT are leaked.

In following table 7, test various paper according to the present invention.These tests are all carried out with tallow8, even so, clearly the paper of with good grounds the present invention coating all make the battery of these paper have outstanding characteristic.Starch is Roquette LAB2273, and gelling agent is Courtaulds 1209, and adhesive is ISP PVP K 120, and additive is Tallow 8amine.

Table 7

						For a long time
																Pulse current intensity			Tested＞12 days			High-speed and continuous
													Paper			SCA	?No.		?DP	?DM	?DT		?DY		?PI
ES			6.3	?15		?6.7	?15.1	?8.6		?6.3
																		v.ES	?100％	?100％				v.ES	?100％
Enso?80	Low-density/low pulse		5.2	?3		?7.1	?15.9	?8.8		?5.7
															v.Enso?80	100％		v.ES	?106％	?105％		v.Enso 80	?100％	v.ES	?101％
NKK??PBDE ?100	High density/high impulse		?6.2	?3		?7.1	?15.9	?8.6		?6.2
														﹠ low-density/low pulse	v.Enso?80	?119％		v.ES	?106％	?105％		v.Enso 80	?109％	v.ES	?102％
Sibillc?Dalle MP75	High density/high impulse		?6.0	?3		?7.1	?15.4	?8.1		?6.2
															?v.Enso?80	?115％		v.ES	?106％	?102％		v.Enso 80	?109％	v.ES	100％
Munksjo 114440	High density/high impulse		?6.3	3		?7.1	?15.6	?8.0		?6.5
															?v.Enso80	?121％		v.ES	?106％	?103％		v.Euso 80	?114％	v.ES	?101％
Singer?70	High density/high impulse		?6.3	3		?6.9	?15.9	?8.0		?6.3
															?v.Enso?80	?121％		v.ES	?103％	?105％		v.Enso 80	?111％	v.ES	?100％

In another following embodiment, high crosslinked cornstarch of standard and various cationic starch compare.Starch type is listed in the following table 8.

Table 8

				Particle mean size
					Starch			Nitrogen	(centimetre)
?Vulca?90	?National	High crosslinked cornstarch	0.0％	0.001
					?LAB2273	?Roquette	Moderate cross-linked cationic farina	0.2％	0.005
?LAB2469	?Roquette	Moderate cross-linked cationic cornstarch	0.2％	0.001
					?620641	?Roquette	Moderate cross-linked cationic wheaten starch	0.2％	0.001

Carry out test as described in Table 9.

Table 9

Test
			????SCA ????Al(AA) ????AW(AA) ????AZ(AA) ????DP(D) ????DY(D)	Continuous LIF is continuous for the pulse of Flash Amps toy	????3R9/1h/0V8 ????1R8/15s/m/0V9 ????3R9/Cont./0V75 ????2R2/4*8m/0V9 ????2R2?/Cont./0V75

Wherein 3R9/1h/0V8 represents by discharging 1 hour 3.9 ohm of every days, up to 0.8 volt of inefficacy.Similarly, 15s/m represented per minute 15 seconds.In the LIF test, battery per hour discharges 4 cycles, 8 minutes each cycles.AA represents the AA battery, and D represents the battery testing with D.

In table 10, shown the influence of change starch and starch thickness to the AA battery.Can see that for the AA battery, must use thicker cross-linked cationic farina, but farina is bad, highly cross-linked cornstarch is also bad.In this table, as being seen in other tables, coconut 20 amine are Crodamet C20 normally.In ensuing table, tallow 5 amine and tallow 8 amine are respectively Crodamet T5 and T8 usually.PRC EMD is from the electrolytic manganese dioxide of the People's Republic of China (PRC), and N65 NMD is from Mexican natural manganese dioxide.

Table 10

Discharge performance
				Starch	Vulca?90	?Roquette ?AB2273	?Roquette?AB2273
Gel	?Courtaulds ?1209	?Courtaulds ?1209	?Courtaulds?1209
				?PVP	?PVP?K120	?PVP?K120	?PVP?K120
Additive	?Coconut????20 ?Amine	?Coconut????20 ?Amine	?Coconut?20?Amine
				Sibille Dalle paper	?MF60	?MF60	?MF60
?gsm	?20	?20	?40
?PRC????EMD/N65 ?NMD	?90/10	?90/10	?90/10
				?SCA	?3.6	?2.3	?3.0
?Al?3R9/1h/0V8	?2.00	?1.60	?1.70
				?AW ?1R8/15s/m/0V9	?150	?122	?144
?AZ ?3R9/Cont./0V7 ?5	?1.80	?1.60	?1.70

In table 11, proved the influence that changes paper thickness in the AA battery, as can be seen, thin paper is favourable, as long as it has necessary structural intergrity.

Table 11

Starch	?Roquette?LAB2273	?Roquette?LAB2273
			Gel PVP additive Munksj* paper gsm thickness HMRA-F EMD/NMD SCA AW 1R8/15s/m/0V9 AZ 3R9/Cont./0V75	Courtaulds 1209 PVP K120 Tallow 8 Amine 100,021 40 .0125 centimetre 10,0/0 6.9 174 2.03	Courtaulds 1209 PVP K120 Tallow 8 Amine 114,440 40 .0150 centimetre 10,0/0 6.0 157 1.95

In table 12, shown that different starch and manganese dioxide in the AA battery form the influence to discharge performance.As can be seen, use all compositions and mixture satisfactorily.

Table 12

Starch	Vulca?90	?Roquette ?LAB2273	?Roquette ?620641	?Roquette ?LAB2469
					Gel	Tylose ?MH200K	?Courtaulds ?1209	?Courtaulds ?1209	?Courtaulds?1209
?PVP	Do not have	PVP?K120	?PVP?K120	?PVP?K120
					Additive	Coconut?20 ?Amine	Tallow????5 ?Amine	?Tallow????5 ?Amine	?Tallow?5?Amine
Munksjo paper	?100021	100021	?300542	?300542
					?gsm	?20	?40	?20	?20
					?PRC?EMD/N65?NMD	?100/0	?100/0	?100/0	100/0
?SCA	?6.6	?6.3	?6.4	?6.7
					?Al?3R9/1h/0V8	?2.38	?3.20	?2.36	?2.44
?AW?1R8/15s/0V9	?182	?168	?176	?180

?AZ ?3R9/Cont./0V75	?2.01	?1.84	?1.94	?2.01
?PRC?EMD/N65?NMD	?50/50	?50/50	?50/50	?50/50
					?SCA	?5.8	?5.5	?6.1	?5.9
?Al?3R9/1h/0V8	?1.61	?1.58	?1.62	?1.65
					?AW?1R8/15s/0V9	?128	?124	?129	?132
?AZ ?3R9/Cont./0V75	?1.56	?1.49	?1.54	?1.56

In table 13, shown that different starch and additive are to the influence of AA battery in two leak tests.The JIS test of AA battery pack comprises by 5 ohm of continuous discharges 48 hours, and observes leakage.For the D battery, by 2 ohmic discharges 48 hours.DAT (test of discharge non-normal condition) test is included in and measures before the leakage, and AA type battery is by 4 weeks of 15 ohmic discharges, and the D battery is by 4 weeks of 5 ohmic discharges.As can be seen, the cross-linked cationic cornstarch has obtained best result.

Table 13

Starch		Vulca?90	?Roquette ?LAB2273	?Roquette ?LAB2273
					Gel		Tylose ?MH200K	?Courtaulds ?1209	?Courtaulds?1209
?PVP		Do not have	?PVP?K120	?PVP?K120
					Additive		Coconut????20 Amine	?Tallow?8?Amine	?Tallow?5?Amine
Paper		NKK?PBDE???70	Munksj*100021	?Munksj*100021
					?gsm		?20	?40
					Leak index (20 batteries)	JIS	?11	?45
Leak index (20 batteries)	DAT	?4	?23

Starch		?Roquette ?620641	?Roquette ?LAB2469
					Gel		?Courtaulds ?1209	?Courtaulds ?1209
?PVP		?PVP?K120	?PVP?K120
					Additive		?Tallow????5 ?Amine	?Tallow?8?Amine
Paper		Munksj* 300542	Munksj*300542
					gsm		?20	?20
					Leak index (20 battery)	JIS	?40	?8
Leak index (20 battery)	DAT	?21	?3

Table 14 has illustrated how the result of JIS test scores ground.Every group of 20 battery, every group sum have constituted leak index.

Table 14

	The leak position			Score
						The outside as seen			50
?1	As seen sheath removes the back			15
					?2	When loosening, sheath can hear exhaust			7
?3A	Seriously	Under the top cover		5
					?3B	Minimum	Under the top cover		3
?4A	Seriously	Under the bottom		5
					?4B	Minimum	Under the top cover		3
?5A	Seriously	Between PVC and the container	Still wet	3
					?5B	Minimum	Between PVC and the container	Still wet	2
?6A	Seriously	Between PVC and the container	Parch	1
					?6B	Minimum	Between PVC and the container	Parch	0

?7A	Seriously	In the space	Still wet	3
					?7B	Minimum	In the space	Still wet	2
?8A	Seriously	In the space	Leak gelling	2
					?8B	Minimum	In the space	Leak gelling	1
?9A	Seriously	In the space	Parch	1
					?9B	Minimum	In the space	Parch	0
?10A	Seriously	The chamber wall perforation		1
					?10B	Minimum	The container perforation		0
?11A	Seriously	The container bottom perforation		1
					?11B	Minimum	The container bottom perforation		0

In table 15, shown the JIS and the DAT result of the test of D battery.Can see that again the cross-linked cationic cornstarch has obtained best result.This table has proved that also shell thickness is that a matter of great account is real.

Table 15

		Shell thickness
						Starch			Vulca?90	?Roquette ?LAB2273	?Roquette ?LAB2469
Gel			Tylose?MH200K	?Courtaulds ?1209	?Courtaulds?1209
						?PVP			Do not have	PVP?K120	?PVP?K120
Additive			Coconut?????20 Amine	?Tallow?5?Amine	?Tallow?5?Amine
						Paper			NKK?PBDE100	?Munksj*114440	?Munksj*300542
?gsm			?40	?40	?20
Leak index (20 batteries)	JIS	0.37 millimeter	224	?60	?44
						Leak index (20 batteries)	JIS	0.46 millimeter	11	?11	?3

In table 16, shown of the influence of different starch of the present invention to the D battery.Again as can be seen, the cross-linked cationic cornstarch has obtained best result.

Table 16

Starch	Roquette?LAB2273	?Roquette?LAB2469
			Gel	Courtaulds?1209	?Courtaulds?1209
?PVP	?PVP?K120	?PVP?K120
			Additive	Tallow?5?Amine	?Tallow?5?Amine
Munksj* paper	100021	?300542
			?gsm	?40	?20
			?PRC?EMD/N65?NMD	?100/0	?100/0
?SCA	?6.3	?6.7
			?DP?2R2/4*8m/0V9	?10.4	?10.7
?DY2R2/Cont./0V75	?7.6	?8.1

Claims (26)

1, a kind of coated paper separators for electrolytic of electrochemical cell, this coating contains starch and additive, it is characterized in that cationic starch has constituted the major part of separator plate coating starch ingredients.

2, dividing plate according to claim 1, wherein additive is to contain polyoxyalkylene, nitrogen compound.

3, dividing plate according to claim 1 and 2, wherein the hydrophile-lipophile balance of additive is less than 17.

4, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein the hydrophile-lipophile balance of additive is less than 14.

5, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein the hydrophile-lipophile balance of additive is less than 11.

6, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein the hydrophile-lipophile balance of additive is less than 9.

7, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein the hydrophile-lipophile balance of additive is greater than 5.

8, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein the hydrophile-lipophile balance of additive is 5-11.

9, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein the hydrophile-lipophile balance of additive is 7-10.

10, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein the hydrophile-lipophile balance of additive is 8-9.

11, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein the hydrophile-lipophile balance of additive is about 9.

12, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein additive is a nonionic.

13, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein the cation element of starch is base with nitrogen, and nitrogen content is to count 0.2-2% (w/w) with the starch dry weight.

14, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein cationic starch has constituted whole starch ingredients basically.

15, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein starch is crosslinked.

16, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein starch is high crosslinked.

17, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein starch is at room temperature water insoluble basically.

18, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein starch is potato, corn or wheaten starch.

19, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein starch is wheaten starch.

20, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein this coating also contains the etherified cellulose as gelling agent.

21, dividing plate according to claim 20, wherein gelling agent can be in room temperature water swelling and gelling immediately basically, and in water, keep stablizing in over a long time.

22, according to claim 20 or 21 described dividing plates, wherein about 20 centipoises of the viscosity of gelling agent (0.02 handkerchief. second) to about 300 centipoises (0.3 handkerchief. second), preferred 50-100 centipoise (the 0.05-0.1 handkerchief. second).

23, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein additive is monobasic and diamine polyoxyalkylene compounds, wherein free alkyl has about 18 carbon atoms, side chain is the polyoxyethylene substituting group, they each average 1 or 2 oxygen ethylene unit is arranged, when compound is diamines, connect by trimethylene between two amine centers.

24, according to the described dividing plate of arbitrary claim in the aforesaid right requirement, wherein under about 20 ℃, paper can be in 4-15 minute, preferred 5-15 minute, more preferably absorbs 50 microlitre water droplets in 5-10 minute.

25, comprise electrochemical cell according to the described dividing plate of arbitrary claim in the aforesaid right requirement.

26, be applicable to the coating mix of production according to the described dividing plate of arbitrary claim among the claim 1-24, described mixture contains cationic starch.