DE1940070C - A method of manufacturing a drying element in which a separator paper containing a gelling agent is placed between the zinc cup and the positive electrode mixture - Google Patents

Description

i 940 070

^^^? ^^ ^toaiBmDdtB · ' ¹ « ^deriva te, be as main component with a

As fiber materials still have a certain strength, fiber material such as Kraft fibers, linter fibers or others

a>"!,. a " crfi ^ _t . Polyvinyl alcohol fibers, used as an adsorption medium

_w S _nr £ r ^ t ^{g IS} l ^ ^{e Verbes!} * ™ g of the rnislht, whereupon the mixture is further mixed and distributed in a coating water adsorbing and water holding agent and the medium. then

Degree of cohesion of a separator layer around which a polymeric precipitation agent, e.g. B. an aqueous one

r ^^ J ^ u ^ f ^ T ^{m ver} «" ^ m solution of sodium methacrylate or polyimine,

f _t r _; w Η «τ ilT ²¹ ^ '** ^life and the solution added, whereupon a piece of paper from the solution

^ Ä ^ T- ^ h ^ T ^ u ^{211 verfces} «™ · is produced / while the fertilizer powder füi

? 5Ä £ " ^e ^? ^{Abe thereby} ' ^{ώβ Fa} -» adsorb the electrolyte on this fiber material

acids and a powdered gelling agent are dis- are in water. In this case it is preferred to use 30 to 2

be pergiert to sine dispersion mixture to 70 to 98 parts by weight of fiber material

form that then add an additive powder for the electrolyte to the dispersion mixture. The

sorbent is added to the pulverulent paper, but can also be in any desired proportions.

Gelling agent to be added to the fibers and produced on 15 nits, which correspond to the

to allow themselves to be fixed, and that the dry element made of the fibers meets the requirements

Chen a Sepamtor paper together with the gelling agent. Any separator paper can be used with the

Jiergesteur wira. desired water absorption capacity, water retention

n the separator papers obtained in this way are the capacity and degree of swelling that are produced.
Powder of the leavening agent for the electrolyte The separator paper produced in this way has the same distribution, and it can have a large amount of the excellent properties mentioned above, but powdery leavening agent for the electrolyte still has some disadvantages. The mechanical strength is introduced into the separator paper. On this wedge of the paper produced in this way is not so high, because we.se the degree of swelling is much higher if the proportion of fibers is lower than the proportion of separator _{paper which absorbs the liquid electrolyte, a 5} gelling agent powder for the electrolyte in the paper. Because of this, there is a risk that the separator paper and the positive electrode paper will tear when a dry element connects. Furthermore, the speed can be built, whereby the work performance is reduced the \ Vasseraufnähme and the water holding capacity; However, the separator paper can also be increased afterwards, which is why the water that has been damaged in the separator paper is never on the positive side, which can lead to an internal short circuit. Electrode mixture migrates. '. _One method of overcoming this disadvantage Ef " ^dun f '" hereinafter with reference to the drawing is to produce a paper according to which a voltage is explained. In the drawing, sizing agent, for example a vinyl acetate emulsion, means a t- 1 g. 1 a section through a drying element of the dispersing medium, e.g. water, for dispersing the Ip AA according to the invention, additive powder for the electrolyte in the fibers serving as H g. 2 a schematic view of a separator adsorption medium, added paper, was comparable in the dry element of FIG. 1. in this method, the Gelierwendet be is. medium powder for the electrolyte with the aid of the i-lg. J and 4 are schematic views of further training fixed 40 sizing agent on the adsorption of the separator papers fuhrungsformen according to the He and no longer separate from the adsorbent, dung, whereby a paper-like material, in which the Ad-H g. 5 and 6 are schematic views of the usual so rptionsmedien are firmly connected to each other, separator papers, can be obtained.

u f ^ei u P ^ia 8 ^{r; lmm of the} temporal changes 45 Another method is that one par-

the water retention capacity of the separator paper with tiell acetylated polyvinyl alcohol fibers as fibers for

the storage of the dry elements, adsorption of the gelling agent powder for the electrolyte

t 1 g. Figure 8 is a graph of the amounts used by the. The polyvinyl alcohol itself is

water absorbed, temperature soluble in water and therefore cannot

9 is a diagram showing the changes in the gelling agent powder for the electrolyte adsorbing

Shows the degree of swelling of the separator paper; on the other hand is partially acetylated polyvinyl alcohol

Fi g. 10 is a diagram showing the capacity of an insoluble in water at room temperature and only at

Shows drying element with intermittent discharge. 60 to 8O ⁰ C soluble. The partially acetylated poly-

The separator paper according to the invention is adsorbed in vinyl alcohol at room temperature

t-orm a uniform mass of fibers la and 55 of the gelling agent powder for the electrolyte effective.

Powders of gelling agents Ib for the electrolyte, if the partially acetylated polyvinyl

posed as it is in F1 g. 2 is shown; The paper is alcohol by heating the paper so made

characterized in that both the fibers and after drying at 60 to 8O ⁰ C, the elec-

the powder evenly throughout the separator paper, the resistance of the fibers themselves can be reduced

are distributed. g ₀ , j _en> while at the same time the strength of the separator

Em preferred method of making a paper can be increased.

Separator paper that is in the form of a uniform A more effective method of increasing the me-mass consists of gelling agent powders for the electrolyte mechanical strength of the separator paper and fibers is described below: in that the separator paper thus made with Powder of a gelling agent for the electrolyte, a Kraft paper or a linter paper or for example natural starches such as corn starch, a water-soluble film, for example a polywheat flour etc., or modified starches or vinyl alcohol film combined. According to this procedure Types of gum such as karaya gum or cellulose can reduce the strength of the gelling powder for

the electrolyte and the fibers made paper when the carbon rod is in the positive electrode with it Help of kraft paper be enhanced; the mixture is used, and the gelling agent powder for Kraft paper side on the side of the positive electrode - the electrolyte in the separator paper is mixed here arranged, then an oxidative cereal layer, whereby a separator layer is formed. There Setting of the powder of a gelling agent for the electrode 5 the separator paper used according to the invention a lytes, especially of types of starch, due to the excellent water absorption rate and gandioxid in the positive electrode mixture prevents an ejection due to the absorption of the liquid. has a marked degree of swelling, it is an ideal sepa-

Furthermore, according to the invention, that from gelling paper can be used in the production of a drying element powder for the electrolyte and fibers produced according to this process.

set separator paper 1 with a conventional paper 14 in FIG. 1 is a drying element of the type AA d can be combined by one side or both sides', whereby a closure 6 made of a plastic, a Kraft paper or the like. With a gelling agent 15 such as polyethylene or polypropylene, for sealing the electrolyte, which in a liquid electrode is provided the opening of the zinc cup. 7 is lytes is dispersed, is coated, whereupon the over- 15 a heat-shrinking plastic tube made of drawn paper is dried (see Fig. 3) and uses polyvinyl chloride or polyethylene. Which can be. In this case the separator paper metal cap 8 serves as a connection for the positive 14 with a coating of the gelling agent for the electrode; the bottom plate 9 serves as a connection for the electrolyte so arranged that this is on the side of the negative electrode. With 10 and 11 are insulating rings, negative zinc electrode is located. If the kraft paper is so labeled 12 is a bottom ring and 13 is an outer ring with a coating of the gelling agent for the electrical jewelry coating.

lytes on both sides as separator paper 14.
half the formation of a complex salt, such as zinc

diamine chloride, braked during storage and 35 ". . .

the service life of the dry element is considerable ^p

can be improved.

Furthermore, according to the invention, a separator - 100 parts by weight of natural starch and 5 to 30 U? -

paper, consisting of at least two layers of weight parts kraft fibers (Kraft Pulp) are each other where mixed each a different mixing ratio between 30 and dispersed in water, followed by 0.1 to Geliermittelpulvern for the electrolyte and fibers 0.005 parts by weight of aqueous a l ° / _o by weight Solution of has to be used. In Fig. 4, the ratio of sodium methacrylate as adsorption medium to the water between the powder and the fibers is 70:30 in the dispersion; furthermore, the first layer 1 ', while the ratio in the two-0.01-0.5 parts by weight of a non-ionic top layer 1 "98: 2. These two layers 35 surfactants, based on 1 part by weight, are combined with one another in that they water in the aqueous dispersion, added,
simultaneously formed into a paper; the so from this aqueous dispersion is with the help of a

The separator paper produced is used in such a way as to combine cylinder and forming paper dimensions the second layer 1 "on the side of the negative machine made a paper. After vacuuming and Zinc electrode lies. 4 ° will drain the paper under a pressure

A method for producing a dry from 10 to 30 kg / cm ² and then pressed at element using the separator paper at a temperature at which the gelling agent powder for the electrolyte according to the invention does not yet undergo gelation in the individual electrolytes, ie described below: below about 70 ⁰ C, with a separator

Zuersi is a positive electrode mixture, the 45 paper α is obtained.

Manganese dioxide, acetylene black, ammonium chloride, zinc- For comparison, starch is found in a liquid

Contains chloride and water as the main components, electrolytes of ammonium chloride, zinc chloride and thoroughly kneaded, whereupon the cylinder is dispersed from the water as the main components, on a positive electrode mixture 3, which is applied by applying side of a sheet of Kraft paper. The so of the mixture on a carbon rod 2 (positive elec- 50 coated Kraft paper is dried, whereby a trode) was produced, with a separator paper 1 conventional separator paper b is produced,
surrounded and placed in a zinc cup 5 (negative elec-

trode) is used, which previously with a paper capacity of these separator papers α and b (built-in disk 4 on the bottom and a liquid electrolyte in elements according to Fig. 1) when stored at 45 ° C from ammonium chloride, zinc chloride and water ver - 55 stated.

would see. In this way, a dry In Fig. 8 are the changes in by 10 g of the

element made. Separator papers α and b absorbed amounts of water

According to a further method, a positive one is given from a liquid electrolyte.
Electrode mixture, the manganese dioxide, acetylene black, In Fig. 9 are the changes over time of the

Ammonium chloride, zinc chloride and water as the 60 degree of swelling of the Separalor papers contains α and b ange main components, thoroughly kneaded, with yellow when the separator papers are surrounded in the liquid Separalor paper and then immersed in an electrolyte,
Zinc provided with a paper disk on the bottom, become the dry elements A and B according to

mug inserted. Then a carbon rod as a positive figure of the type AA is hewn together using the separator electrode in the middle of the positive electrode paper α or b , so the integments are inserted, whereby a drying element is formed and the leakage rate of the second will. In this case, the liquid electrolyte migrates to electrolytes of these dry elements; the hn positive Hlekirode mixture in the separator results are given in Tables 1 to 3.

Table 1

Duration of discharge down to 0.85 V with intermittent discharge via a load resistor of 10 ohms (30 minutes / day)

Dry element Immediately after
the production 6 months at 45 ° C
stored A.
B. 430 minutes
380 minutes 400 minutes
330 minutes

Table 2

Number of drying elements with faulty tension, based on 100 drying elements operating at 45 ° C were stored

Table 3

Dry element 6 months at 45 ° C
stored 12 months at 45 ° C
stored A.
B. 0
2 1
5

Dry element 30 days
ditched 60 days
ditched A.
B. 0
10 8th
32 _N.

Number of dry elements that have leaked, related

on 50 dry elements, which ^{discharge 24 hours at 20 0} G over an external load resistance of 10 ohms and then at 3O ⁰ C for the specified time

were left standing

The discharge curves of the drying elements A and B, which were discharged intermittently (30 minutes / day with a load resistance of 10 ohms), are shown in FIG. 10 specified.

The results show that the separator paper used in the present invention has a high water absorption capacity and an excellent water holding capacity as well as an excellent degree of swelling hai and that the drying element with the separator paper according to the invention has a lower internal resistance stand, a higher discharge capacity, a lower drop in performance after storage and a good leak has consistency.

1 sheet of drawings

Claims (8)

-. . _. The invention relates to a method for patent claims: production of a dry element with a zinc 1. Process for the production of a drying cup as a negative electrode and with one in the element with a zinc cup as a negative EIek zinc cup arranged positive electrode mitrode and with an arrangement in the zinc cup with manganese dioxide as a depolarizer, in which th positive electrode mixture with manganese between the zinc cup and the positive electrode dioxide as a depolarizer, in which a separator paper is placed between the mixtures, the Zinc cup and the positive electrode mixture contains a gelling agent that when used together a separator paper is placed which gels with the electrolyte. Contains gelling agent, which when meeting io dry elements with a zinc cup than negative gelled with the electrolyte, thereby creating an electrode and a positive one arranged in it indicates that fibers and a powdered electrode mixture with manganese dioxide as depolar shape Gelling agents are dispersed in water, saior and an intermediate zinc cup and positive to form a dispersion mixture that separator paper arranged in this way Then the dispersion mixture has an adsorption layer on one side of which a layer of gelling agent is applied means is added to the powdery «gelation» is known as is used in the German patent means deposit on the fibers and on writing 952 728 a method for making a to let this set, and that described from the dry element, in which on the Sepa fibers together with the gelling agent a rator paper a starch-flour mixture on one side on separator paper will be produced. 30 is brushed, rolled or sprayed. In the USA.- 2. The method according to claim 1, characterized in patent 2 923 757 is a similar dry drawing, that described as a powdery gelling agent min element with a separator paper that desiens a substance from the group of natural an adhesive layer and then a gelling agent Starches, the modified starches, the layer bears. This gelling agent gels when used with Types of rubber and the cellulose derivatives used 25 which come into contact with electrolytes. will. A known type of separator paper is in the 3. The method according to claim 1 or 2, characterized in that F 1 g. 5 and 6 shown. It is made of Japanese paper, characterized in that at least one type of filter paper, kraft paper or fiber paper (Linteraus of the group of Kraft fibers (Kraft pulp), linter paper) 16 and is one or both sides with a fibers (linter pulp) and partially acetylated poly paste 17 made from natural starch or synthetic vinyl alcohol fibers be used. table material that is in a liquid 4. The method according to one or more of the electrolytes is distributed and dried; the separator saying 1 to 3, characterized in that the paper is between the positive electrode mixture Separator paper made up of several layers and the negative zinc electrode designed as a cup is, with each layer inserted a different mixture and used as a separator layer, according to ratio between the powdery gelling agent, the liquid electrolyte in the separator paper absorbent and the fibers. is beer. 5. The method according to one or more of the arrival in such a separator has only 1.5 to speaking 1 to 4, characterized in that a 2.0 parts by weight of natural starch or a synthe-position of the separator paper with a layer of paste on tables 40 1 part by weight of Japanese paper, filter kraft paper, linter paper or a water-based paper, kraft paper or linter paper, which is why the soluble films are layered on top of one another and the separator paper is so swollen after absorption in the zinc cup that that of the liquid electrolyte is not sufficient. If the separator paper is attached to the inner wall of the zinc half, the separator paper cannot lie firmly with the cup. 45 positive electrode mixture and the negative zinc 6. The method according to one or more of the electrode are connected, and the contact resistor claims 1 to 5, characterized in that the stand between the two is high. Furthermore, the one or both sides of a normal separator part of the fiber material in the separator paper is high, and paper, e.g. B. a Kraft paper, with a Geliei- the water holding capacity of the fiber material is averaged for the electrolyte to be coated and 50 ringer than the water holding capacity of the positive paper treated in this way with a layer of an electrode mixture. Therefore, the water of the separator paper, which is made of powdered gelling liquid electrolyte, which is absorbed in the fiber material and fibers, is bound, migrates during the storage of the dry element to the and that the separator produced in this way in the zinc side of the positive electrode mixture , whereby the cup is arranged in such a way that a gelling 55 internal resistance of the separator layer increases,
middle layer on the inner wall of the zinc cup With the usual paper-lined dry elements, the internal resistance increases 7. The method according to one or more of the an adverse effect on the discharge capacity, the Proverbs 1 to 3, characterized in that the service life and freedom from leaks of the drying element dispersion mixture of fibers and gelling agent 60 thes, as explained above. To one more a high polymer precipitant, e.g. B. would take the internal resistance to prevent, it is emergency sodium methacrylate or polyimine, is added. agile, the proportion of fiber material in the separator 8. Method of reducing one or more of the paper, and improving the Claims 1 to 3, characterized in that it is the degree of swelling and the water holding capacity one of the dispersion mixture of powdery 65 necessary, the proportion of the gelling agent for the elec-gelling agent and fibers still a vinyl acetate trolyte, d. H. natural starch and synthetic emulsion added as a sizing agent. see paste in the separator paper to increase. It was difficult, however, to implement these measures in a sepa-