CH385308A - Assembly comprising an electrode and at least one separator, for galvanic element - Google Patents

Assembly comprising an electrode and at least one separator, for galvanic element

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Publication number
CH385308A
CH385308A CH439362A CH439362A CH385308A CH 385308 A CH385308 A CH 385308A CH 439362 A CH439362 A CH 439362A CH 439362 A CH439362 A CH 439362A CH 385308 A CH385308 A CH 385308A
Authority
CH
Switzerland
Prior art keywords
assembly
fibers
electrode
sub
separator
Prior art date
Application number
CH439362A
Other languages
French (fr)
Inventor
Spreter Victor
Haeusler Rudolf
Original Assignee
Spreter Victor
Haeusler Rudolf
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Spreter Victor, Haeusler Rudolf filed Critical Spreter Victor
Priority to CH439362A priority Critical patent/CH385308A/en
Publication of CH385308A publication Critical patent/CH385308A/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Victor Spreter et Rudolf Häusler, :Geneve, sont mentionnes comme etant les inventeurs L'invention a trait ä un ensemble comprenant une electrode et au moins un separateur, pour Ele ment galvanique, ladite electrode etant constituee par un Support poreux conducteur de 1'electricite dont une partie au moins des pures contient une matiere active. Victor Spreter and Rudolf Häusler, Geneva, are mentioned as being the inventors The invention relates to an assembly comprising an electrode and at least one separator, for galvanic element, said electrode being constituted by a porous support of which at least part of the pure contains an active ingredient.

Les elements galvaniques modernes, en particu- lier les elements secondaires alcalins ou acides, com- prennent des electrodes dans lesquelles la matiere active, par exemple 1'hydroxyde de nicket pour des elements alcalins, ou 1'oxyde de plomb pour des elements acides, est deposee dans les pures d'un Support conducteur poreux. Ces Supports poreux sont constitues par agglomeration sous pression dune poudre metallique, d'oü 1e nom generique d'elec- trodes frittees qu'on donne aux electrodes ainsi r6ali- s6es. Dans une premiere categorie de Supports, la matiere poreuse enrobe une armature conductrice solide, par exemple un feuillard perfore, un fin treillis ou un tissu, destinee ä conferer ä 1'electrode une Bonne resistance mecanique. Dans une seconde cate- gorie, 1e Support ne comporte pas d'armature ; il est constitue uniquement par la poudre metallique qui est frittee en plaque. Cette derniere categorie offre l'avantage d'etre capable de fixer plus de matiere active, puisque 1e volume qui, dans les supports de la premiere categorie, est occupe par 1'armature, est occupe dans ce cas par de la matiere poreuse ; si bien que, ä masse egale de matiere active, 1e volume et 1e poids de 1'electrode ainsi constituee, sont dimi- nu6s. Mais la fragilite des electrodes saus armature est elevee, ce qui limite fortement les possibilites d'emploi des e1ements galvaniques constitues avec de telles electrodes. Modern galvanic elements, in particular alkaline or acidic secondary elements, include electrodes in which the active material, for example nickel hydroxide for alkaline elements, or lead oxide for acidic elements, is deposited in the puree of a porous conductive support. These porous supports are formed by agglomeration under pressure of a metal powder, hence the generic name of sintered electrodes given to the electrodes thus produced. In a first category of supports, the porous material coats a solid conductive reinforcement, for example a perforated strip, a fine mesh or a fabric, intended to give the electrode good mechanical resistance. In a second category, the Support has no reinforcement; it is constituted solely by the metal powder which is sintered into a plate. This last category offers the advantage of being able to fix more active material, since the volume which, in the supports of the first category, is occupied by the reinforcement, is occupied in this case by porous material; so that, for an equal mass of active material, the volume and the weight of the electrode thus constituted are reduced. But the fragility of the electrodes without armature is high, which strongly limits the possibilities of use of the galvanic elements constituted with such electrodes.

Dans 1e but d'eviter la coüteuse operation du frittage dune poudre metallique, an a cherche ä utiliser une armature conductrice poreuse dopt la porosite soit suffisamment e1evee pour constituer directement 1e Support de la matiere active. C'est ainsi qu'on a propose une electrode constituee par une armature en graphite poreux. Cependant, 1e gra- phite poreux est fragile ; en outre, 1'epaisseur de cette electrode ne peut, pour des raisons de tenue m6ca- nique, etre inferieure ä une limite determinee, d'oü, pour un element galvanique constitue avec une 6lec- trode de ce type, une resistance interne et un encom brement minimums imposes. In order to avoid the costly operation of sintering a metal powder, an attempt has been made to use a porous conductive armature whose porosity is high enough to directly constitute the support for the active material. Thus, an electrode constituted by a porous graphite reinforcement has been proposed. However, porous graphite is brittle; in addition, the thickness of this electrode cannot, for reasons of mechanical strength, be less than a determined limit, from which, for a galvanic element constitutes with an electrode of this type, an internal resistance and a minimum size imposed.

En outre, une electrode du type connu doit, lors de son montage Jans un element galvanique, etre separee de 1'electrode voisine par un separateur, iso- lant et poreux, dopt 1e röte est d'empecher un con- tact direct tout en permettant ä 1'electrolyte de bai- gner 1'ensemble. La presence du separateur impose une limite inferieure ä la distance separant deux electrodes voisines, par consequent ä la resistance interne de 1'element et ä son encombrement. In addition, an electrode of the known type must, when it is mounted in a galvanic element, be separated from the neighboring electrode by an insulating and porous separator, the purpose of which is to prevent direct contact while allowing the electrolyte to bathe the assembly. The presence of the separator imposes a lower limit on the distance separating two neighboring electrodes, consequently on the internal resistance of the element and on its size.

L'invention a pour but d'eliminer ces inconve- nients en proposant un ensemble comprenant une electrode et au moins un separateur, pour e1ement galvanique, dann lequel ladite electrode est consti- tu6e par un Support poreux conducteur de 1'elec- tricit6 dopt au moins une partie des pures contient une matiere active, caracterise par 1e fait que ce Support est constitue par un ensemble de fibres qui sont, au moins Sur leur surface, conductrices de 1'electricite et entrelacees de maniere ä menager entre elles des interstices minuscules constituant ces pures, ce Support etant revetu, Sur au moins une partie de sa surface exterieure, dune mince couche de matiere isolante poreuse constituant ledit s6pa- rateur. Quelques formes d'execution de 1'invention sont decrites ci-apres, ä titre d'exemple. The object of the invention is to eliminate these drawbacks by proposing an assembly comprising an electrode and at least one separator, for a galvanic element, in which said electrode is constituted by a porous electrically conductive support at least a part of the pure contains an active material, characterized by the fact that this Support is constituted by a set of fibers which are, at least on their surface, conductors of electricity and intertwined in such a way as to form between them tiny interstices constituting these pure, this support being coated, on at least part of its outer surface, with a thin layer of porous insulating material constituting said separator. Some embodiments of the invention are described below, by way of example.

Ort peut utiliser, pour realiser 1e support,. un feutre tres fin et tres poreux en matiere synthetique, prealablement metallise de fapn ä rendre conduc- trice chacune des fibres synthetiques dont il est constitue. Ort can use, to realize the first support,. a very fine and very porous felt in synthetic material, previously metallized so as to make each of the synthetic fibers of which it is made conductive.

Un feutre qui convient particulierement bien est, par exemple, celui qui est connu sous 1e nom com- mercial de Vlieseline (marque deposee). Ce feu- tre est metallise, par n'importe quel procede connu, de maniere que chaque fibre soit recouverte dune couche de metal, y compris celles qui sont ä 1'inte- rieur de la masse de feutre. Il est avantageux pour cela de recourir ä un procede de metallisation chi- mique en phase liquide, comme la reduetion d'un sel du metal ä deposer, ou ä un procede de m6tal- lisation en phase gazeuse, comme la decomposition d'un compose volatil du metal ä deposer. Il convient ensuite d'epaissir cette premiere couche de mAal par un depöt galvanique, afin d'ame1iorer ä la fois la conductivite electrique du feutre metallise ainsi consti- tue et sa resistance mecanique. Ce depöt galvanique peut etre execute en une Beule opdration ou en plu- sieurs etapes, avec des metaux identiques ä celui qui constitue la premiere couche ou, pour des rai- sons d'adherence notamment, avec des metaux dif- fdrents. La derniere couche, cependant, doit etre adaptee ä 1'usage prevu pour 1'electrode. Par exem- ple si 1'electrode est destinee ä etre incorporee dans un element galvanique secondaire alcalin, cette der- niere couche au moins Sera constituee de nickel, de fer, de cadmium ou encore d'argent. Si 1'electrode est destinee ä etre incorporee dans un element gal- vanique secondaire aride, rette derniere couche Sera constituee par du plomb ; si elle est destinee ä un element galvanique primaire, la demiere couche sera en zinc. On obtient de rette fagon un support qui est extremement poreux et qui a une stabilite m6ca- nique suffisante. Les pures de ce Support sont ensuite remplis de matiere active de la meme maniere qu'une electrode frittee usuelle, par exemple d'hydroxyde de nickel pour une 61ectrode destinee ä un element Cd/Ni ou Fe/Ni, d'oxyde de plomb ou de peroxyde de plomb pour une electrode destinee ä un 616ment au plomb. Puis 1'ensemble est recouvert, en partie au moins, dune tres mince couche dune matiere isolante poreuse, par exemple de polyethylene, cons- tituant un separateur. A felt which is particularly suitable is, for example, that which is known under the trade name of Vlieseline (registered trademark). This felt is metallized, by any known method, so that each fiber is covered with a layer of metal, including those which are inside the mass of felt. It is advantageous for this to resort to a process of chemical metallization in the liquid phase, such as the reduction of a salt of the metal to be deposited, or to a process of metallization in the gaseous phase, such as the decomposition of a compound. volatile metal to be deposited. This first layer of mAal should then be thickened by galvanic deposition, in order to improve both the electrical conductivity of the metallized felt thus formed and its mechanical strength. This galvanic deposition can be carried out in a single operation or in several stages, with metals identical to that which constitutes the first layer or, for reasons of adhesion in particular, with different metals. The last layer, however, must be suitable for the intended use of the electrode. For example, if the electrode is intended to be incorporated in an alkaline secondary galvanic element, this last layer at least will be made up of nickel, iron, cadmium or even silver. If the electrode is intended to be incorporated in an arid secondary galvanic element, its last layer will be lead; if it is intended for a primary galvanic element, the last layer will be zinc. In this way, a support is obtained which is extremely porous and which has sufficient mechanical stability. The portions of this Support are then filled with active material in the same way as a usual sintered electrode, for example nickel hydroxide for an electrode intended for a Cd/Ni or Fe/Ni element, lead oxide or of lead peroxide for an electrode intended for a lead element. Then the assembly is covered, in part at least, with a very thin layer of a porous insulating material, for example polyethylene, constituting a separator.

Cela peut s'obtenir de diverses manieres. Par exemple en trempant 1'electrode, chargee de mauere active comme il a 6t6 dit plus haut, dans un pre- mier liquide forme par un melange de polyethylene et d'oxyde de polyethylene, tous deux dissous dans un solvant, en la sechant pour obtenir une tres mince couche de polyethylene parsemee d'oxyde, puis en la trempant dans un second- liquide, par exemple de 1'eau, qui ne dissout que 1'oxyde de polyethylene, de fagon ä creer des pures Jans la tres mince couche de matiere isolante ainsi constituee. Plusieurs autres procedes existent pour realiser de telles couches de matieres isolantes poreuses tres minces. This can be achieved in various ways. For example, by soaking the electrode, loaded with active mauer as mentioned above, in a first liquid formed by a mixture of polyethylene and polyethylene oxide, both dissolved in a solvent, drying it to obtaining a very thin layer of polyethylene strewn with oxide, then soaking it in a second liquid, for example water, which dissolves only the polyethylene oxide, so as to create pure layers in the very thin layer. of insulating material thus formed. Several other processes exist for producing such layers of very thin porous insulating materials.

Cette tres mince couche de matiere isolante po- reuse evite que la matiere active s'echappe des pures du Support tout en permettant ä 1'electrolyte de 1'e16- ment galvanique de baigner cette matiere active. Elle constitue par consequent 1e separateur Jans 1'element galvanique constitue avec cette 61ectrode. 0n a de la Sorte un ensemble qui comprend une 61ectrode ä haute teneur en matiere active, ä Bonne stabilite mecanique et qui permet de realiser un 61e ment galvanique ä faible resistance interne et ä en- combrement reduit, puisque 1e separateur de cet ensemble est plus mince que tout separateur usuel utilise dans les realisations traditionnelles. This very thin layer of porous insulating material prevents the active material from escaping from the pure of the Support while allowing the electrolyte of the galvanic element to bathe this active material. It therefore constitutes the separator in the galvanic element constituted with this electrode. There is thus an assembly which comprises an electrode with a high content of active matter, with good mechanical stability and which makes it possible to produce a galvanic electrode with low internal resistance and reduced bulk, since the separator of this assembly is more thinner than any usual separator used in traditional designs.

Il est possible d'accroitre encore la porosite du Support en detruisant, apres 1e depöt galvanique, 1'äme en matiere synthdtique des fibres metallisees de fapn que cette destruction fasse dclater locale- ment 1e revetement mAallique en y provoquant des dechirures mettant 1'interieur des fibres metalliques en communication avec l'exterieur : 1e Support a alors la forme d'un feutre dont chaque fibre est metallique et a la forme d'un tube pourvu de mul tiples ddchirures locales. La matiere active peut alors etre deposee nun seulement dans les minuscules interstices menages entre les fibres, mais aussi ä 1'interieur meme des fibres tubulaires metalliques. Un moyen pour realiser cette destruction consiste ä faire subir au feutre mAallise un chauffage ä une temperature depassant la temperature de d6compo- sition de la matiere synthetique constituant 1'äme de chaque fibre, les gaz produits par cette d6composi- tion thermique faisant eclater 1e revetement m6talli- que de res fibres. Il est avantageux, pour donner au Support une Bonne stabilite mecanique, que les diverses fibres du feutre initial en matiere synthetique soient colldes ensemble par une resine synthetique. C'est pr6cise- ment 1e ras du feutre connu sous 1e nom de Vlie seline et c'est ce qui fait 1'interet de ce materiau. It is possible to further increase the porosity of the Support by destroying, after the galvanic deposition, the synthetic material core of the metallized fibers so that this destruction causes the metal coating to burst locally by causing tears therein putting the inside metal fibers in communication with the outside: the first Support then has the shape of a felt, each fiber of which is metallic and has the shape of a tube provided with multiple local tears. The active material can then be deposited not only in the tiny interstices made between the fibers, but also inside the metallic tubular fibers themselves. One means of carrying out this destruction consists in subjecting the metallic felt to heating at a temperature exceeding the decomposition temperature of the synthetic material constituting the core of each fiber, the gases produced by this thermal decomposition causing the coating to burst. metallic fibers. It is advantageous, to give the support good mechanical stability, that the various fibers of the initial synthetic material felt are bonded together by a synthetic resin. It is precisely the level of the felt known under the name of Vlie seline and this is what makes the interest of this material.

0n peut aussi prendre, pour constituer 1'ensemble de fibres isolantes, un tissu. Dans ce ras, le collage des fibres les unes aux autres est encore plus indi- que, rar un tissu a toujours moins de rigidite m & a- nique qu'un feutre. 0n can also take, to constitute 1'ensemble of insulating fibers, a fabric. In this case, the bonding of the fibers to each other is even more indicated, for a fabric always has less mechanical rigidity than a felt.

Claims (5)

REVENDICATION Ensemble comprenant une electrode et au moins un separateur, pour element galvanique, ladite & c- trode etant constituee par un support poreux condue- teur de 1'electricite dopt au moins une partie des pures contient une matiere active, caracterise par 1e fait que ce support est constitue par un ensemble de fibres qui sont; au moins -Sur leur surface, conduc- trices de 1'electricite et entrelacees de maniere ä menager entre elles des interstices minuscules consti- tuant res pures, ce Support dtant revetu, Sur au moins une Partie de sa surface exterieure, dune mince couche de matiere isolante poreuse constituant ledit separateur. SOUS-REVENDICATIONS 1. Ensemble selon la revendication, caracterise par 1e fait que ledit ensemble de fibres conductrices est constitue par un ensemble de fibres isolantes qui est metallise de fagon que- chacune de ces fibres soit recouverte d'un revetement conducteur. CLAIM Assembly comprising an electrode and at least one separator, for galvanic element, said & c- trode being constituted by a porous electrically conductive support adopts at least a part of the pure contains an active material, characterized by the fact that this support is constituted by a set of fibers which are; at least -on their surface, conductive of electricity and intertwined so as to form between them tiny interstices constituting res pure, this support being coated, on at least a part of its external surface, with a thin layer of porous insulating material constituting said separator. SUB-CLAIMS 1. Assembly according to claim, characterized in that said assembly of conductive fibers consists of an assembly of insulating fibers which is metallized so that each of these fibers is covered with a conductive coating. 2. Ensemble selon la revendication et la sous- revendication 1, caracterise par 1e fait que les fibres dudit ensemble de fibres conductrices ont la forme de minuscules tubes metalliques qui sont pourvus de microdechirures locales mettant 1'interieur de ces tubes en communication avec 1'exterieur, de Sorte que 1'interieur de ces tubes constitue une Partie des- dits pores. 2. Assembly according to claim and sub-claim 1, characterized by the fact that the fibers of said assembly of conductive fibers have the form of tiny metal tubes which are provided with local micro-tears placing the interior of these tubes in communication with the exterior, so that the interior of these tubes constitutes part of said pores. 3. Ensemble selon la revendication et les sous- revendications 1 et 2, caracterisd par 1e fait que ledit ensemble de fibres isolantes est un feutre. 3. Assembly according to claim and sub-claims 1 and 2, characterized by the fact that said assembly of insulating fibers is a felt. 4. Ensemble selon la revendication et les sous- revendications 1 et 2, caracterise par 1e fait que ledit ensemble de fibres isolantes est un tissu. 4. Assembly according to claim and sub-claims 1 and 2, characterized by the fact that said assembly of insulating fibers is a fabric. 5. Ensemble selon la revendication et les sous- revendications 1 ä 4, caracterise par 1e fait que les fibres dudit ensemble de fibres isolantes sont Lides ensemble par une resine synthetique. 5. Assembly according to claim and sub-claims 1 to 4, characterized in that the fibers of said assembly of insulating fibers are held together by a synthetic resin.
CH439362A 1962-04-10 1962-04-10 Assembly comprising an electrode and at least one separator, for galvanic element CH385308A (en)

Priority Applications (1)

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CH439362A CH385308A (en) 1962-04-10 1962-04-10 Assembly comprising an electrode and at least one separator, for galvanic element

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CH439362A CH385308A (en) 1962-04-10 1962-04-10 Assembly comprising an electrode and at least one separator, for galvanic element

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CH385308A true CH385308A (en) 1964-12-15

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0022409A2 (en) * 1979-07-06 1981-01-14 SORAPEC SA Société de Recherches et d'Applications Electrochimiques Electrode structure for electrochemical generator
FR2482788A2 (en) * 1980-05-19 1981-11-20 Sorapec Battery electrode mfr. - by chemically plating copper or nickel on a porous or fibrous mineral or organic eliminatable substrate
FR2535116A2 (en) * 1982-10-22 1984-04-27 Composites Electrolytiques Ste Electrodes made of composite materials

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0022409A2 (en) * 1979-07-06 1981-01-14 SORAPEC SA Société de Recherches et d'Applications Electrochimiques Electrode structure for electrochemical generator
EP0022409A3 (en) * 1979-07-06 1981-01-28 Sorapec, Sarl, Societe De Recherche Et D'applications Electrochimiques Electrode structure for electrochemical generator
FR2472842A1 (en) * 1979-07-06 1981-07-03 Sorapec ELECTRODE STRUCTURE FOR ELECTROCHEMICAL GENERATOR
FR2482788A2 (en) * 1980-05-19 1981-11-20 Sorapec Battery electrode mfr. - by chemically plating copper or nickel on a porous or fibrous mineral or organic eliminatable substrate
FR2535116A2 (en) * 1982-10-22 1984-04-27 Composites Electrolytiques Ste Electrodes made of composite materials

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