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United States Patent [191 ‘ [111 33,802,921 Urry ' ' [451 Apr

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United States Patent [191 ‘ [111 33,802,921 Urry ' ' [451 Apr United States Patent [191 ‘ [111 33,802,921 Urry ' ' [451 Apr. 9, 1974 [54] SEPARATOR FOR PRIMARY GALVANIC' 3,089,914 5/1963 Carmichael et al ............... 136/131 CELLS 3,494,801 2/1970 Urry ............................... .. 136/133 [75] Inventor: Lewis F. Urry, North Olmsted, Ohio 3,048,645 8/1962 Ruben....; ..................... .. 136/100 M [73] Assignee: Union Carbide Corporation, New Primary Examiner-Donald L. Walton York, NY. _ Attorney, Agent, or Firm-Robert C. Cummings [22] Filed: Mar. 28, 1972 [21] Appl. No.: 238,921 ‘[57]. ’ ' ABSTRACT A separator for primary galvanic cells particularly of [52] US. Cl. ........... ..136/100 M, 136/131, 136/145 the type in which the depolarizer-cathode mix has a [51] Int. Cl. .......................................... .. H01m 3/00 - :high moisture content comprises two plies of paper. [58] Field of Search ......... .. 136/100 R, 100 M, 107, One ply is. adjacent to and in contact with the depola rizer-cathode and is folded over that portion, thereof 136/123,125,128,130,131-,145,133 de?ning one boundary of a free space in the cell. A [56] References Cited second ply is in contact with the anode of the cell and UNITED STATES PATENTS extends into the free space. The anode contacting ply 1 is of paper more bibulous than the cathode contacting 1,640,488 8/1927 Deibel et al. ..................... .. 136/131 ply. 1,654,038 12/1927 Deibel .............. .. 136/131 615,292 12/1898 Maas ................................. .. 136/123 ‘7 Claims, 2 Drawing Figures 3,802,921 1 . 2 SEPARATOR FOR PRIMARY GALVANIC CELLS piercing rod. In this construction virtually all of thecell electrolyte is added by way of the wet mix, which is - This invention relates to primary galvanic cells, par therefore much wetter than that used to mold bobbins. ticularly of the type having a relatively large quantity . Both the placement under pressure of wet mix in the of electrolyte, and is more speci?cally directed to an container and the insertion of the cathode collector rod improved separator for such cells. present problems in smearing contamination of the in Although the most widely used primary galvanic cells side of the container anode with mix and possible rup are commonly referred to as “dry cells”, of course they turing or penetrating by mix fines of the separator liner are not dry since they employ an aqueous electrolyte. previously placed in the cell container. However, the electrolyte is immobilized in the cell, For various reasons zinc chloride and magnesium cy being absorbed within the depolarizer-mix, which is the lindrical cells are‘ preferably made as lined cells on cell cathode, and within the separator interposed be equipment of the same type used to make lined Lec tween the cathode and the anode of the cell. The sepa lanche' cells. Whereas the wettest Leclanche’ mixes run rator in addition to retaining some of the cell electro about 20 percent water maximum by weight, the zinc lyte serves the function of providing physical, separa chloride and magnesium cell mixes may run as high as tion between anode and cathode to prevent short cir 28-35 percent water by weight. The mix contamination cuiting of the cell. ‘ problem is accentuated in the latter mixes because of By far the most widely used primary galvanic cell sys the higher water content. In the manufacture ofa mag tem is the Leclanche' in which the consumable anode nesium cell, for example, a sheet of paper is placed into is zinc‘, the depolarizer-cathode is manganese dioxide, 20 a magnesium tube or cup to line its internal walls. Wet and the electrolyte is an aqueous solution of zinc chlor mixis then injected into the container, and the collec ide and ammonium chloride. Separators for this system tor rod is driveninto the mix. A continuing quality have engaged the attention of the industry for many problem is experienced with such cells. No matter how years, and the suggestions for separators have run the or where the mix‘ or mix particles come into direct gamut from sawdust to sophisticated ?lms. Generally 25 contact with the magnesium wall, the disadvantages ac the most successful separators, and those most widely cruing therefrom are serious. Thus internal short cir used in this system today, include a highgrade paper cuits may occur or perforation corrosion of the magne with a starch or gel coating on one or both sides, the sium wall may take place. Both of these phenomena separator being placed in the cell with the starch or gel have been observed when a single sheet of plain paper adjacent to and in contact with the zinc anode. 30 has been used as separator between the magnesium Although as indicated the Leclanche' type dry cell has wall and the mix. The use of a gel'or starch coated enjoyed great success, recently increased attention is paper or of ?lms (forexample methylcellulose) in mag being paid to other systems or modifications of the sys nesium cells has introduced other problems due pri tem to provide characteristics not obtainable in the marily to lowered diffusion rate of reaction products in Leclanche'systemfFor example considerable effort has 35 the cell without solving the contamination problem. In been made to substitute for the zinc anode an anode of the zinc chloride cell system, where gel coatedpaper is magnesium. The magnesium anode offers the prospect generally preferred over plain paper, the mix contami of higher voltage than can be obtained with a zinc an nation problem also exists. Actually it has been found ode. Even more recently, the substitution of aqueous that in all three cell systems in which lined cells areas zinc chloride solution for the mixed ammonium chlor 40 sembled from wet mix by extrusion or compression into ide and zinc chloride solution used as electrolyte in the a lined can contamination is a problem,'being worst > Leclanche' system has come under intensi?ed investiga with the magnesium system and least with Leclanche’. tion. Both the magnesium cell and the zinc chloride cell employ a larger quantity of aqueous electrolyte (than 45 Study or the problem has shown that mix'contamina is required in the conventional Leclanche' cell) because tion of the anode occurs in- a variety of ways and has ‘ in both, cell reactions consume water and service may several causes. Considerable pressure is exerted on and be limited by insufficient watercontent. " by the mix during mix injection, mixpiercing,.a‘nd col Commercial conventional Leclanche'cylindrical cells lector rod insertion. Some free electrolyte, carrying are of two main types. In the “pasted" cell the wet cath 50 mix ?nes, is expressedfrom a portion'of the mix (espe ode depolarizer mix is impact or pressure molded to . cially the bottom) during these pressure steps. The free give a cylindrical “bobbin“ 0r “dolly” containing a electrolyte ?ows‘ into the paper'separator and may also central carbon collector rod or “pencil”. This bobbin tend to flow outward past the separator overlap and up is later inserted into a cylindrical zinc anode container ward into the free space above the mix. The paper is “can" or “cup" together with a flowable separator 55 subject to possible stretching or tearing under pres? paste or colloidal mass which is cooked or otherwise‘ sure, especially when wet. Mix particles may thus pene gelled to givean immobilized separator member be trate past the ?bers even when the original dry paper_ tween the zinc can and the mix bobbin. Relatively dry appears free of_ thin spots or pin holes. mixes give the best bobbins, so in this construction a ‘ A grosser'form of mix contamination can occur in the substantial amount of the total cell electrolyte is added 6.0 upper portion of the cell during mix injection, mix by way of the separator paste. piercing, and electrode insertion. During mix insertion - In the “lined“ cell the separator is applied to the in excess mix tends to .?ow up past the insertion'nozzle side wall ,of the zinc can either as an adherent ?lm or and this can smear on the inside of the can when the coating or as an inserted layer ofcoated paper, for ex nozzle is withdrawn. The mix piercing rod is usually ro ample. The wet cathode mix is extruded or rammed 65 tated and this can throw mix outagainst the can wall. into position to ?ll a major portion of the lined can, and All of these operations including electrode insertion the central carbon collector rod is then inserted di‘ can produce loose particles or chunks of mix on the top rectly into the rammed mix or into a hole made by a surface of the compressed mix, which may later fall, I 3,802,92l 3 . 4 I against the anode wall and stick there as the cell is han I extending outwardly of the cell. The cell is closed by a dled. ' ~ vented Washer 16 and a metal cover 18 which is se In addition to the mechanical demands placed on the cured to an end'of the container anode 10. A metal ter separator, it must also freely imbibe and retain electro 'minal 20 is provided on'the cathode collector 14. lyte in position against the anode in order to insure full The depolarizer-cathode 12, as shown does not com utilization of the anode surface and to maintain a low pletely fill the container-anode 10, so that between the electrolytic resistance to current flow through the sepa depolarizer-cathode l2 and the washer 16 a free space rator.v Mechanical considerations call for a thick, 22 is provided. Separating the depolarizer-cathode 12 ‘strong, dense, slow-wetting, high wet-strength separa from the walls of the container-anode 10 is the separa tor paper, whereas electrochemical considerations re ll) tor of the invention which, as shown, comprises two quire a thin, soft, open structure, highly bibulous and plies 24, 26 of paper.
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