CH351311A

CH351311A - Flat galvanic cell and process for its manufacture

Info

Publication number: CH351311A
Authority: CH
Inventors: Walter Krueger Ralph; George Soltis Daniel
Original assignee: Union Carbide Corp
Priority date: 1958-04-16
Filing date: 1959-01-07
Publication date: 1961-01-15

Description

Cellule galvanique plate et procede pour sa fabrication Cette invention a pour objets une cellule galva- nique plate et un procede pour la fabrication de rette cellule. Flat galvanic cell and process for its manufacture This invention relates to a flat galvanic cell and a process for the manufacture of such a cell.

La cellule galvanique selon 1'invention est carac- t6risee en ce qu'elle comprend une anode m6tallique consumable, un d6polarisant mouil16 d'dlectrolyte disposd de part et d'autre de 1'anode et separe de celle-ei par un s6parateur, une cathode collectrice flexible et impermeable aux liquides, qui est en con- tact avec 1e d6polarisant et qui est r6unie herm6ti- quement ä une chemise flexible et impermdable aux liquides de maniere ä former avec celle-ei une enve- loppe feuilletee, sce116e de fagon 6tanche, 1e contact avec la cathode etant susceptible d'etre dtabli ä tra vers une perforation de la chemise, et un conducteur fixe ä 1'anode et s'6tendant vers 1'exterieur hors de la chemise scellee. The galvanic cell according to the invention is characterized in that it comprises a consumable metal anode, a depolarizer wetted with electrolyte placed on either side of the anode and separated from it by a separator, a flexible and liquid-impermeable collector cathode which is in contact with the depolarizer and which is hermetically joined to a flexible and liquid-impermeable jacket so as to form therewith a laminated envelope, sealed in a watertight manner , contact with the cathode being capable of being made through a perforation in the jacket, and a conductor fixed to the anode and extending outwardly from the sealed jacket.

Les dessins annexds representent, ä titre d'exem- ple, deux formes d'execution de la cellule selon 1'in- vention. The accompanying drawings show, by way of example, two embodiments of the cell according to the invention.

La fig. 1 est une coupe verticale dune cellule ; la fig. 2 represente, sdpares les uns des autres, les el6ments formant 1'enveloppe de la cellule ; la fig. 3 est une vue en plan, avec arrachement partiel, desdits eldments assembl6s ; la fig. 4 est une vue en perspective de la cellule ; la fig. 5 illustre schematiquement la fabrication en continu de cellules plates. en grande Serie ; la fig. 6 est une coupe, semblable ä la fig. 1, dune autre forme d'execution ; la fig. 7 illustre une Serie de Stades de 1'assem- blage des e16ments dune cellule. fig. 1 is a vertical section of a cell; fig. 2 represents, separated from each other, the elements forming the envelope of the cell; fig. 3 is a plan view, partially broken away, of said assembled elements; fig. 4 is a perspective view of the cell; fig. 5 schematically illustrates the continuous manufacture of flat cells. in large series; fig. 6 is a section, similar to fig. 1, of another form of execution; fig. 7 illustrates a series of stages in the assembly of the elements of a cell.

La fig. 1 represente, en coupe, une cellule galva- nique plate. Cette cellule comprend une mince feuille ou segment 10 d'un m6tal Bon conducteur, par exem- ple d'aluminium, disposd entre deux couches super- posdes, ä savoir une pellicule enveloppante 12, faite dune matiere impermdable au liquide, et une couche collectrice ou collecteur cathodique 16, la pellicule 12 etant percde dune ouverture 14 qui d6bouche Sur 1e Segment m6tallique 10 et ä travers laquelle un contact de connexion peut etre 6tabli avec ce Seg ment. Une anode 20 est contenue ä l'intdrieur dune enveloppe form6e par deux pellicules de matiere se- paratrice 19, un fil conducteur 61ectrique 22 6tant fixe ä rette anode ; ei, de part et d'autre des pelli- cules 19, sont dispos6es deux pastilles 18 et 24 faites d'un d6polarisant moui116 d'electrolyte. Le con- ducteur 22 est pourvu d'un isolement dlectrique 23. Une garniture d'6tanch6it6 21 est RTI ID="0001.0270" WI="11" HE="4" LX="1678" LY="1724"> pr6vue Sur 1e fil 22 ä 1'endroit oü ce fil est attach6 ä 1'anode 20 ; et les pellicules separatrices 19 constituent des bar- rieres entre 1e fil 22 et les pastilles de d6polarisant 18 et 24. La pellicule enveloppante 12 forme 1'enve- loppe exterieure de la cellule et 1'entoure complete- ment, les portions marginales de rette pellicule 12 6tant scellees, de pr6ference par soudage ä chaud, autour de la periph6rie de ladite cellule, comme an 1e voit clairement en 26 ä la fig. 4. Le conducteur 61ectrique isole 22 fait saillie hors de la matiere scel- lee 26, comme representd. fig. 1 represents, in section, a flat galvanic cell. This cell comprises a thin sheet or segment 10 of a good conductive metal, for example aluminum, placed between two superposed layers, namely an enveloping film 12, made of a material impermeable to liquid, and a collecting layer. or cathode collector 16, the film 12 being pierced with an opening 14 which opens onto the metallic segment 10 and through which a connection contact can be established with this segment. An anode 20 is contained inside an envelope formed by two films of separating material 19, an electrical conductor wire 22 being fixed to this anode; ei, on either side of the films 19, are arranged two pellets 18 and 24 made of a depolarizer wetted with electrolyte. The conductor 22 is provided with an electrical insulation 23. A sealing gasket 21 is provided on the RTI ID="0001.0270" WI="11" HE="4" LX="1678" wire 22 where that wire is attached to anode 20; and spacer films 19 form barriers between wire 22 and depolarizer pellets 18 and 24. film 12 being sealed, preferably by heat sealing, around the periphery of said cell, as clearly seen at 26 in FIG. 4. Insulated electrical conductor 22 protrudes from seal material 26, as shown.

Ort voit ä la fig. 3 que 1e collecteur 16 presente des dimensions legerement superieures ä celles du Segment 10 et qu'il ddborde Sur lui suffisamment pour qu'il puisse convenablement etre fixd par lami- nage, par exemple par une soudure ä chaud ou ä 1'aide dune rolle ou ciment se fixant par pression, ä la pellicule enveloppante 12. Le collecteur 16 recouvre 1e segment 10 sann se souder ä celui-ci. Ort sees in fig. 3 that manifold 16 is of slightly larger dimensions than Segment 10 and that it overlaps sufficiently so that it can be suitably secured by lamination, such as by heat welding or rolling or cement attaching by pressure to the enveloping film 12. The manifold 16 covers the segment 10 without being welded thereto.

La fig. 5 illustre comment la cellule peut etre fabriqude en grande Serie. La pellicule 12 est sous forme dune longue Bande continue, et des ouvertures 14 y sont pratiquees ä des intervalles reguliers. A la fig. 5, les ouvertures ont 6t6 representdes comme pratiqu6es en alternance de maniere ä se trouver d'un cöte et de 1'autre de deux cellules successives. Ceci facilite ensuite 1'assemblage de plusieurs cellules sous forme (Tun empilage ou Batterie de cellules mont6es en serie, sans qu'il soit besoin de ddcouper la Bande en trongons. De meine, les ouvertures pourraient eire dispos6es en vue (Tun montage en parallele ou en vue (Tune formation en Batterie de type s6rie- parallele. fig. 5 illustrates how the cell can be manufactured in large series. The film 12 is in the form of a long continuous strip, and openings 14 are made therein at regular intervals. In fig. 5, the openings have been represented as practiced alternately so as to be on one side and on the other of two successive cells. This then facilitates the assembly of several cells in the form of a stack or battery of cells mounted in series, without the need to cut the strip into sections. or in sight (a series-parallel type Battery formation.

Les Segments condueteurs 10 sont pos6s Sur la pellicule 12 transversalement ä la longueur de celle-ci de maniere qu'on puisse y avoir acces ä travers 1'ou- verture 14. Les collecteurs cathodiques flexibles 16 sont plac6s de maniere ä recouvrir les Segments 10 et sont fixes par leurs Bords ä la pellicule envelop- pante 12, de pref6rence par soudage ä chaud et sous pression. Sur chaque anode 20, ä laquelle est reli6 un fil conducteur isol6 22, an dispose des pastilles de depolarisant 18 et 24 Sur chacune des faces, cette anode 6tant separ6e desdites pastilles par la matiere s6paratrice 19. Chaque ensemble ainsi forme est place Sur une moiti6 environ d'un collecteur 16, et Fon replie alors 1e reste de la Bande 12 par-dessus lesdits ensembles, puis an les scelle convenablement, par exemple par soudage ä chaud Sur toute la peri- ph6rie desdits ensembles, ä la portion non repli6e de ladite Bande 12, ce qui forme des poches 6tanches ä 1'humiditd qui enveloppent totalement lesdits en- sembles. Chaque fil isole 22 est revUu dune matiere d'6tancheite 21 resistant ä 1'humidit6, telle que 1e ciment de vinyle ou 1'asphalte, ä 1'endroit oiz il tou- che 1'anode. Au point oü ce fil isold 22 traverse 1'en- veloppe, celle-ci est scelMe hermdtiquement Sur 1'iso- lant 23, afin qu'un joint 6tanche ä 1'humidit6 soit assure en tous points de 1'enveloppe de la cellule. The conductive segments 10 are laid on the film 12 transversely to the length of the latter so that they can be accessed through the opening 14. The flexible cathode collectors 16 are placed so as to cover the segments 10 and are secured at their edges to the wraparound film 12, preferably by heat and pressure welding. On each anode 20, to which an insulated conductive wire 22 is connected, there are depolarizing pellets 18 and 24 On each of the faces, this anode being separated from the said pellets by the separating material 19. Each assembly thus formed is placed On one half of a collector 16, and the remainder of the Strip 12 is then folded over the said assemblies and then suitably sealed, for example by heat welding. said Strip 12, thereby forming moisture-proof pockets which completely envelop said assemblies. Each insulated wire 22 is faced with a moisture resistant sealing material 21, such as vinyl cement or asphalt, where it contacts the anode. At the point where this insulated wire 22 passes through the shell, the shell is hermetically sealed to the insulation 23, so that a moisture-tight seal is provided at all points of the cell shell. .

Des essais de mise sous tension ont 6t6 effectu6s apres quatorze jours de conservation Sur des empi- lages de cellules selon la technique ant6rieure et sur des empilages de cellules telles que celles d6crites. La frequence avec laquelle an observe des tensions inf6rieures ä la normale apres une certaine p6riode d'emmagasinage peut etre consid6ree comme une in- dication satisfaisante de la frequence de 1'existence de cellules individuelles n'ayant pas 6t6 completement scelkes et ayant perdu des quantitds excessives d'hu- midite. De tels essais effectuds Sur des empilages reprAentant plus de dix mille cellules de chaque modele essaye ont indiqu6 que, gräce ä la construe- tion d6crite, la frequence des observations de cellules imparfaitement RTI ID="0002.0274" WI="11" HE="4" LX="510" LY="2322"> scell6es a 6t6 rdduite ä une valeur inf6rieure au quart de celle obtenue avec les cellules construites selon la technique ant6rieure. Tensioning tests were carried out after fourteen days of storage on stacks of cells according to the prior technique and on stacks of cells such as those described. The frequency with which subnormal voltages are observed after a certain period of storage may be taken as a satisfactory indication of the frequency of the existence of individual cells which have not been completely sealed and which have lost significant quantities. excessive humidity. Such tests carried out on stacks representing more than ten thousand cells of each model tested indicated that, thanks to the construction described, the frequency of observations of cells imperfectly RTI ID="0002.0274" WI="11" HE=" 4" LX="510" LY="2322"> sealed was reduced to a value less than a quarter of that obtained with the cells constructed according to the prior art.

Outre cet avantage remarquable du point de vue quahtatif, 1e present proced6 de fabrication proeure une economie moyenne de matiere de 6,9 pour cent par rapport aux procedes antdrieurs. De plus, ce pro- ced6 se preie ä un degr6 remarquable aux techniques de fabrication en grande s6rie et de montage ä la chaine, de Sorte qu'aucun des avantages des procedes antdrieurs n'a 6t6 sacrifie pour assurer la quakte amelior'e et la reduction du prix de revient obtenues par 1e pr6sent procede. In addition to this remarkable qualitative advantage, the present manufacturing process provides an average material saving of 6.9 percent over prior processes. In addition, this process lends itself to a remarkable degree to mass production and assembly-line techniques, so that none of the advantages of prior processes have been sacrificed to ensure improved quality and reduction in the cost price obtained by the present process.

La fig. 6 repr6sente une autre forme d'exeeution. Cette cellule comporte une anode mäallique consu- mable 20, de preference en zinc, recouverte (Tun separateur spongieux 19. Une pastille de depolarisant 24, mouill6e d'electrolyte, est disposde de chaque cöte de 1'anode 20. Ces el6ments de la cellule sont contenus (ans une enveloppe feuilletee, qui com- prend un colleeteur cathodique flexible electrique- ment conducteur 16, pouvant etre fait dune mince feuille de matiere plastique conductrice, un Segment metallique 10 en contact 61ectrique avec 1e collecteur 16 et une chemise ext6rieure flexible, dlectriquement isolante et impermeable aux liquides, 12, qui pre- sente une ouverture 14 permettant d'etablir une con- nexion electrique avec 1e segment 10 et, par Suite, avec 1e collecteur cathodique 16. Une - connexion electrique est etablie avec 1'anode 20 par un con- ducteur 6lectrique 22, qui peut avantageusement eire fait d'un metal en forme de ruban fix6 ä ladite anode par soudage, rivetage ou autre moyen. Une couche 23 dune substance adMsive Oectriquement isolante, teile qu'un composd de caoutchouc, est pr6- vue au niveau du joint etabli entre 1e condueteur 22 et 1'anode 20. L'assemblage des elements de la cellule representee ä la fig. 6 ressort de la fig. 7. 0n voit ä la fig. 7 que Fenveloppe de cellule, qui a 6t6 formee dune maniere analogue ä celle indiquee ä la fig. 3, peut etre repli6e sur elle-meme, et que ses Bords complementaires peuvent etre scelles ä chaud, comme represente en 28 ä la fig. 7 (A). 0n notera qu'il existe un joint continu 6tanche entre les Bords reunis du collecteur 16 et de la chemise ext6- rieure 12, bien que 1e Segment 10 ne soit scell6 ni au collecteur, ni ä la chemise 12. 0n peut mainte- nant ins6rer (ans 1'enveloppe 1'anode 20 qui a 6t6 envelopp & d'un separatur 19, pouvant avantageuse- ment consister en une pellicule dune matiere RTI ID="0002.0546" WI="9" HE="4" LX="1840" LY="1871"> spon- gieuse, teile que la m@thylcellulose, port & par un Support, tel que du papier. Comme an voit ä la fig. 7 (B), 1e fil conducteur 22 s'6tend vers 1'extd- rieur de 1'enveloppe, dont les Bords marginaux 30 peuvent maintenant etre scelles ä chaud 1'un ä 1'autre et ä la substance adhesive 23, appliqu6e auparavant au fil 22. Un melange depolarisant 24, avantageuse- ment sous forme de pastilles moul6es d'avance, peut maintenant etre place dann 1'enveloppe (fig. 7, (C)), et 1'on peut sceller les Bords marginaux restants, comme indique en 32 (D) pour terminer la cellule. Avant de terminer 1e scellement, an effectue ä 1'int6- rieur de 1'enveloppe un vide partiel, qui s'est avere comme ayant un effet favorable sur la cellule. fig. 6 represents another form of execution. This cell comprises a consumable metal anode 20, preferably made of zinc, covered with a spongy separator 19. A depolarizing pellet 24, wetted with electrolyte, is arranged on each side of the anode 20. are contained (in a laminated envelope, which comprises an electrically conductive flexible cathode collector 16, which may be made of a thin sheet of conductive plastic material, a metal segment 10 in electrical contact with the collector 16 and a flexible outer jacket, electrically insulating and impermeable to liquids, 12, which presents an opening 14 making it possible to establish an electrical connection with the first segment 10 and, subsequently, with the first cathode collector 16. An electrical connection is established with the anode 20 by an electrical conductor 22, which may advantageously be made of metal in the form of a strip attached to said anode by welding, riveting or other means. A layer 23 of an electrically insulating adMsive substance, such as a rubber compound, is provided at the level of the joint established between the conductor 22 and the anode 20. The assembly of the elements of the cell represented in FIG. 6 spring from fig. 7. It is seen in fig. 7 than the cell envelope, which has been formed in a manner analogous to that shown in FIG. 3, can be folded back on itself, and its complementary edges can be heat sealed, as shown at 28 in FIG. 7 (A). It will be noted that there is a continuous watertight seal between the joined edges of the manifold 16 and the outer jacket 12, although the Segment 10 is sealed neither to the manifold nor to the jacket 12. (in the casing of the anode 20 which has been wrapped in a separator 19, which can advantageously consist of a film of a material RTI ID="0002.0546" WI="9" HE="4" LX="1840 "LY="1871"> spongy, such as methyl cellulose, carried by a Support, such as paper. exterior of the envelope, the marginal edges 30 of which can now be heat sealed to each other and to the adhesive substance 23, previously applied to the wire 22. A depolarizing mixture 24, preferably in the form of pre-molded pellets, can now be placed in the envelope (Fig. 7, (C)), and the remaining Marginal Edges can be sealed, as shown at 32 (D) to complete the cell. Before completing the sealing, a partial vacuum is drawn inside the envelope, which has been found to have a favorable effect on the cell.

Le procede d6crit se prete tout particulierement ä la fabrication de cellules galvaniques plates du type Leclanch6 comprenant une chemise faite en une pellicule en chlorure de polyvinyle et une ca- thode collectrice faite en une pellicule de resine vi- nylique impregnee de carbone. 0n peut aussi faire usage, pour la pellicule formant chemise, de tonte matiere souple, electriquement isolante, imperm6able aux liquides mais permdable aux gaz, choisie par exemple parmi les suivantes : r & ines de vinyle, caout- chouc halogene, resines de vinylidene, derivds de la cellulose, polyethylene et Polyesters An glycol et de 1'acide terephtalique. Une ou plusieurs de .ces me- mes matieres, rendues conductrices par des moyens courants, peuvent aussi etre utilis6es pour former 1e collecteur cathodique. Une condition importante, dans 1e choix des matieres ä utiliser, est que tous les constituants soient compatibles, mais lorsque cette restriction a 6te observee, il peut etre fait usage de tonte combinaison des matieres ci-dessus pour la pellicule enveloppante et 1e collecteur cathodique. 0n utilise de prefdrence 1e zinc pour 1'anode, 1e bioxyde de manganese comme d6polarisant et 1e chlorure d'ammonium comme electrolyte, mais an pourrait faire usage d'anodes en magnesium, en aluminium ou en manganese avec les electrolytes et depolarisants respectifs approprMs. Un m6tal approprie pour la pellicule 10 est 1'aluminium, mais tont autre m6ta1 desire peut eire utilisd ; et un conducteur electrique fait d'un laiton etam6 connect6 avec 1'anode s'est avere comme satisfaisant, bien qu'on puisse faire usage d'un m6tal quelconque ne formant pas un cou- ple prejudiciable avec 1'anode. L'anode peut affecter des formes diverses (feuille, grille, poudre) et 1e sepa- rateur qui 1'entoure peut eire fait de tonte matiere separatrice spongieuse, par exemple de Papier revetu de methylcellulose. The process described lends itself most particularly to the manufacture of flat galvanic cells of the Leclanch6 type comprising a sleeve made of a film of polyvinyl chloride and a collecting cathode made of a film of vinyl resin impregnated with carbon. It is also possible to make use, for the film forming a shirt, of any flexible material, electrically insulating, impermeable to liquids but permeable to gases, chosen for example from the following: vinyl resins, halogen rubber, vinylidene resins, derivatives of cellulose, polyethylene and Polyesters An glycol and terephthalic acid. One or more of these same materials, made conductive by common means, can also be used to form the cathode collector. An important condition in selecting the materials to be used is that all the constituents be compatible, but where this restriction has been observed, any combination of the above materials may be used for the wraparound film and the cathode collector. Preferably, zinc is used for the anode, manganese dioxide as the depolarizer, and ammonium chloride as the electrolyte, but magnesium, aluminum, or manganese anodes could be used with the appropriate respective electrolytes and depolarizers. A suitable metal for the film 10 is aluminum, but any other desired metal can be used; and an electrical conductor of tinned brass connected with the anode has been found to be satisfactory, although use may be made of any metal which does not form a detrimental couple with the anode. The anode can take various forms (sheet, grid, powder) and the separator which surrounds it can be made of any spongy separating material, for example paper coated with methylcellulose.

Les cellules fabriqu6es par 1e procdd6 d6crit peu- vent etre empilees sous forme de Batterie des types Serie , parallele ou s6rie-parallele y>. Une fa- @on commode d'empiler les cellules consiste ä sou- mettre 1'empilage ä une forte Pression en bout, au moyen dune armature metallique. 0n peut aussi deformer les empilages, par exemple leur Bonner la forme d'arcs ou de cercles, de fagon ä les adapter ä tonte application particuliere. The cells manufactured by the process described can be stacked in the form of a battery of the series, parallel or series-parallel y> types. A convenient way of stacking the cells is to subject the stack to strong end pressure, by means of a metal reinforcement. The stacks can also be deformed, for example into arcs or circles, to suit your particular application.

Claims

CLAIMS I. Flat galvanic cell, characterized by the fact that it comprises a consumable metal anode, a wet depolarizer of electrolyte placed on either side of the anode and separated from it by a separator, a collecting cathode flexible and impermeable to liquids, which is in contact with the depolarizer and which is hermetically joined to a flexible and impervious jacket of ma- RTI ID="0003.0274" WI="8" HE="3" LX="274" LY="2298"> ny to form with the latter a sheet envelope &, sealed in a leaktight fashion, the first contact with the cathode being capable of being established through a Perforation of the jacket, and a conductor fixed to 1 ' anode and extending outward from the sealed jacket. 1I. Process for the manufacture of the cell according to claim I, characterized in that it consists in establishing a laminated envelope composed of a flexible and liquid-impermeable outer jacket and a flexible and liquid-impermeable collecting cathode, applied against the face interior of said jacket, to place on said cathode a layer of a depolarizer wetted with electrolyte whose dimensions are smaller than those of the jacket, to successively superimpose on the layer of depolarizer a consumable metallic anode and a second layer of depolarizer, to cover this last layer with a portion of the laminated envelope in such a way that a part of the collecting cathode comes into contact with said last layer and, finally, to seal between them the portions in contact of the laminated envelope. SUB-CLAIMS 1. Cell according to claim 1, characterized in that the sleeve is sealed only by portions of this sleeve overlapping, the cathode thus being entirely enveloped by the sleeve.

2. Cell according to claim I, characterized in that a film of metal is interposed between the cathode and the jacket.

3. Cell according to claim I, characterized in that said separator consists of a spongy material soaked in electrolyte.

4. Cell according to claim I, characterized in that the cathode is constituted by a film of vinyl resin impregnated with carbon.

5. Process according to claim 11, characterized in that the jacket consists of a continuous strip of film which is pierced with openings and on which several collector cathode segments are applied, these segments being regularly spaced.

6. Process according to claim II and sub-claim 5, characterized in that the laminated envelope is folded over the depolarizer and the contacting portions of this envelope are mutually sealed.

7. Process according to claim 11 and sub-claims 5 and 6, characterized in that the contacting portions of the casing are constituted solely by peripheral edges of said film which extend beyond the cathode segments. . B.

Process according to claim II and sub-claim 5, characterized in that Segments of metal film are intercalated between the sleeve and the cathode Segments, the dimensions of these Segments of metal film being smaller than those of the Segments of cathode.

9. Process according to claim II, characterized in that the casing is sealed by heat welding.