FR2634594A1 - ELECTROCHEMICAL GENERATOR WITH ALKALINE ELECTROLYTE AND NEGATIVE ELECTRODE OF ZINC - Google Patents

ELECTROCHEMICAL GENERATOR WITH ALKALINE ELECTROLYTE AND NEGATIVE ELECTRODE OF ZINC Download PDF

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Publication number
FR2634594A1
FR2634594A1 FR8810013A FR8810013A FR2634594A1 FR 2634594 A1 FR2634594 A1 FR 2634594A1 FR 8810013 A FR8810013 A FR 8810013A FR 8810013 A FR8810013 A FR 8810013A FR 2634594 A1 FR2634594 A1 FR 2634594A1
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France
Prior art keywords
electrochemical generator
generator according
indium
organic compound
ppm
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Legal status (The legal status 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 status listed.)
Granted
Application number
FR8810013A
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French (fr)
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FR2634594B1 (en
Inventor
Rene Vignaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CIPEL WONDER
WONDER
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CIPEL WONDER
WONDER
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Publication date
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Priority to FR8810013A priority Critical patent/FR2634594B1/en
Priority to CH2387/89A priority patent/CH679713A5/fr
Priority to DE3923751A priority patent/DE3923751C2/en
Priority to JP1192421A priority patent/JPH0279367A/en
Publication of FR2634594A1 publication Critical patent/FR2634594A1/en
Application granted granted Critical
Publication of FR2634594B1 publication Critical patent/FR2634594B1/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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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

Abstract

Générateur électrochimique à électrolyte alcalin et à électrode négative de zinc, caractérisé par le fait que ladite électrode de zinc exempte de mercure, de cadmium et de plomb, contient un mélange comportant 0,005 % à 1 % en poids d'indium et 1 à 1000 ppm d'au moins un composé organique de stabilisation choisi parmi les composés polyfluorés du type fluoroalcool éthoxylé et les composés du type sulfure d'alcoyle et d'alcool polyéthoxylé. Un tel générateur présente des performances (courbes C et D) au moins égales à celle d'un générateur où le zinc est amalgamé à 5 % (courbe B)Electrochemical generator with alkaline electrolyte and negative zinc electrode, characterized in that said zinc electrode free of mercury, cadmium and lead, contains a mixture comprising 0.005% to 1% by weight of indium and 1 to 1000 ppm at least one organic stabilization compound chosen from polyfluorinated compounds of the ethoxylated fluoroalcohol type and compounds of the alkyl sulfide and polyethoxylated alcohol type. Such a generator has performance (curves C and D) at least equal to that of a generator where the zinc is amalgamated at 5% (curve B)

Description

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: %uaTZuoo UoT7uaAU7,1 usoas 'alid el slaT.ua9$9d saldwaxa,p e v7 V e:9w np spTod ne zaoddea ued % z'D za % ú01 aú,uO asTxdwoo %sa npuT ua dnaua. eT sa widd OOZ:a 0I GE aaua asTdfzoz:sa anbTuEBio asodwoa z7pnp anaua9 eI 'aouaia9aad ae T9IXOqT4aúod looolv,P;a a7.osie,p aunrjns ad.. r.p ssofwoc sa1a 9 ?jxot4^ LooiLeioJonl; Gd n-p saaoni$úod sasodwo3 G 7;wved isTcto uoTesilTqe;s ap anb:ueBxo asodwoo un SUTOW ne,p wdd OJOC E T;s wn-puT,p SpTod ua % T ' % G000 %uasiuoo 'quold oz ap Za =nTw=?o ap '_noau anp aduaxa DuIz ap apo;oDola a:pel anb -:e; aT _ed gs7_o o 'ouIz ap aAIT:!EfU apo-oaZl? es Za u!Tj a1úIooaI e GnbwTu!oo uoa-, zrnaeagugs un aGqo _nod e uoTzuaAuT 9euasad eq *% 5 sgwe2lewe sa aUTz al no sa-pt d saI anb sGoueo; ad sauaw sal:ueuuasad ste u joId -u 'nT.aTUp u 'anzaa. Tu ueuaiuoz au;:P zuawa;ne ',,adoid GTtd, ae. 'ouTz ap aA-efau Gpo0J;,CG M aUTTieTe a-,id aun asieat a? Za -ua-UGAUC;oUT ao; aITAg,p znq inod e uoItuaAuT asuGssJd e7 AaT9 snld 7Te9;uex-r.noo al anb aJTp-e -zsa,z 'ainp snTd Z7e29 uo Ie;; TTlos el anb:uawaz:au snld zueune,p 01 Toa za 'e:;7d 'l ap uoTsua ap neGAtu np iuawassTeqe un wTeSSTJeedde IT nlosga zze79 Zu7z np uoTsoUoD e'l ap aWalqoJd al Ts 'anb %e;%suoo aaL e T 'ssuuapozgad sea xnap sal suea 'spTod ua % I 'C % 100'0 ap a2eueuaanod un suep,TJúxoM;xo'd TooTep Ta alúODTie,p ainJ$ns adúz np gsodwoa *%rne un o0 ú29 Z-Y-_i sT5ueMJ; ZaAaaq uos suep qsodcad e assaaapu-ewap PT sanalITe aed ' 9Toqozo9 I aooonl; adXL np qzonTj$Tod anbTueao gsoduoo un,p ou7z ne ziodded aed spTod ua % I IC % O0'0 ap a8ezuazanod un %ueJciczou; ua _u-z ua apcDaCoI aun,p uoTpsiT:-qtes ap apgDoad un  :% uaTZuoo UoT7uaAU7,1 usoas' alid el slaT.ua9 $ 9d saldwaxa, p e v7 V e: 9w np spTod zaoddea ued% z'D za% ú01 au, uO asTxdwoo% sa npuT ua dnaua. and its Widding OOZ: OI GE AAUA asTdfzoz: its anbTuEBio asodwoa z7pnp anaua9 ei 'aouaiaaad ae T9IXOqT4aúod looolv, p. a7.osie, p aunrjns ad .. r.p ssofwoc sa1a 9xot4 ^ LooiLeioJonl; Gd np saaoni $ úod sasodwo3 G 7; wved isTcto uoTesilTqe; s ap anb: ueBxo asodwoo a SUTOW ne, p wdd OJOC AND; s wn-puT, p SpTod ua% T '% G000% uasiuoo' quold oz ap Za = nTw ? ap 'au au p p p p p p p p p p p p p p p p p p p p p p p p p p p p p au p au au au au au au p au p p p p p p p p p p p p p p p p p p p p p p p? Where did you go from here ?: Where did you go? es Za u! Tj a1ooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooh ad sauaw sal: ueuuasad ste u joId -u 'nT.aTUp u' anzaa. You are here on the following day: adoid GTtd, ae. or, in the case of GMP, CG MUTUTERY, has the same as? Za -ua-UGAUC; oUT ao; aITAg, p znq inod e uoItuaAuT asuGssJd e7 AaT9 snld 7Te9; uex-r.noo al anb aJTp-e -zsa, z 'ainp snTd Z7e29 uo Ie ;; TTlos el anb: uawaz: au snld zueune, p 01 Toa za 'e:; 7d' l ap uoTsua ap neGAtu np iuawassTeqe a wTeSSTJeedde IT nlosga zze79 Zu7z np uoTsoUoD el ap aWalqoJd al Ts' anb% e;% suoo aaL e T 'ssuuapozgad sea xnap sal suea' spTod ua% I 'C% 100'0 apa2eueuaanod a suep, txxoM; xo'd TooTep Ta alúODTie, p ainJ $ ns adúz np gsodwoa *% rne a o0 ú29 ZY-_i sT5ueMJ ; ZaAaaq uos suep qsodcad and assaaapu-ewap PT sanalITe aed '9Toqozo9 I aooonl; adXL np qzonTj $ Tod anbTueao gsoduoo a, p or7z not ziodded aed spTod ua% I IC% O0'0 ap a8ezuazanod a% ueJciczou; ua _u-z ua apcDaCoI aun, p uoTpsiT: -qts ap apgDoad a

--C ú -9 s-ietue;,;aaa.q u^s suep 3nbTpui e assauapueuap e-  --C ú -9 s-ietue;,; aaa.q ues suep 3nbThis assuapueu e

TesTP'eU un amd anzT;suos zuauwBez0u ze 'aTUIMU ISG H IUOTpUU aT1a  TesTs an amd anzT; suos zuauwBez0u ze 'aTUIMU ISG H IUOTpUU aT1a

C UOITAUa aZ @GZUsTidwoosa u -C UOITAUa at @GZUsTidwoosa u -

no/za 'auoqJeo ap saWoZe El UOITAU e a aiozoI 7ozpea un 2sa d -  no / za 'auoqJeo ap saWoZe El UOITAU e aiozoI 7ozpea a 2sa d -

aouia;a7d aaaouia; a7d aa

001 z aE@aua sTadwoo $sa u -001 z aE @ aua sTadwoo $ sa u -

Oú Za 'ahi/Xa o!Te IMOTPp unWhere Za 'ahi / Xa o! Te IMOTPp a

no aLúi TeTipeJ un 'GTITIU uCu no U aTT 0 'aúsmI Tu 1ieTpe un qsa H -  no alUi TeTipeJ a 'GTITIU uCu no U aTT 0' aUsmI You are a qsa H -

: alanbel suep alnwioj: alanbel suep alnwioj

H3- (-HD- HD-O) -( HO) -S-HH3- (-HD-HD-O) - (HO) -S-H

(r) atnumoj el e puodai anbTuejo asodwoo T.aID 'uoTeSTTI!GI ap a@U2T!e a GaTUenb aun sung  (r) atnumoj and the puodai anbTuejo asodwoo T.aID 'uoTeSTTI! GI ap a @ U2T! e a GaTUenb aun sung

SE -SE -

HO - Z'O HD'HO) - ( O = n D -HO - Z'O HD'HO) - (O = n D -

ú) Gin=lok uT e puodai OZ anbtum2o asodwoo zTpGl 'uo7.oesT7ea9 ap a ueTIA awsa7s-.c: aun suua *Z;s r-, a;ua @ousga, d ap,? -:a aua sIJdwoo;sa b E ap UISTOA suaJagad ap @a 01 a T aiZua STIJdWoo sa d g a 9 ai;ua ou.ajayad ap 'OE 5a F a;ua syidwoo.sa u : alantul suep H0_ o %HZ) - dE... _ T-UE L (E) a7nwic, elT puodai anbTueujo asofioo -.paj 'uot:isTegai ap aueTJeaA apuooas aun suea H0 t (oHED) H ED i DL : sodwoo ne ^uepuodsa-oo auuaúou aIzTenoaTow assiew aun oaae 0O HO VI(O7HO) z HE3 IEZ OI za  ú) in G G G G G an an an an as as::::::::::::::::::::::::::::::::::::. -: aa sIJdwoo, its b U apaISTOA suaJagad ap @a 01 a taiZua STIJdWoo sa dga 9 ai; ua ou.ajayad ap 'OE 5a Fa ua syidwoo.sa u: alantul suep H0_ o% HZ) - dE ... _ T-UE L (E) a7nwic, elT puodai anbTueujo asofioo -.paj 'uot: isTegai ap aueTJeaA apuooas aun suea H0 t (oHED) H ED i DL: sodwoo ne ^ uepuodsa-oo auuaúou aIzTenoaTow assiew aun oaae OO HO VI (O7HO) HE3 IEZ OI za

H0 VI(O0VHE) 7H EH E1O 93H0 VI (O0VHE) 7H EH E1O 93

-u: eulg ua ia;Joduoo -uauale, znad II I ap -ISToA zsa b aT7anbeT suep H0 (COHZJ7 7H E0 ú1 9O aTnwioj el e ajpuoda ai s ^nad IT aldwaxa ied EZT ea 0 aizua aouajagjd ap ' ze c ajaua sTidwoo sa b e 'z ap u-STOA aouaa:gad ap -a 0,a I ae;ua sTduidoo zsa d %a 9 aGUZa GDuagagJf ap '? 2a V a7 ua SiJd-00 ZSa U -7S  -u: eulg ua ia; Joduoo -auauale, znad II I ap -ISToA zsa b aT7anbeT suep H0 (COHZJ7 7H E0 ú1 9O aTnwioj el ajpuoda ai s ^ nad IT aldwaxa ied EZT ea 0 aizua aouajagjd ap 'ze c ajaua sTidwoo his / her / his / her / his / her / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / /

865Sú9Z865Sú9Z

D'autres caractéristiques et avantages de la présente invention  Other features and advantages of the present invention

apparaîtront au cours de la description suivante de modes de réalisation  will be apparent from the following description of embodiments

donnés à titre illustratif mais non limitatif. Le dessin annexé comporte une figure unique montrant des courbes de décharge de piles de l'art antérieur et d'une pile selon l'invention. On prépare une pile alcaline A sans mercure, sans cadmium et sans plomb, mais dont l'électrode négative est constituée par de la poudre de zinc vierge dispersée dans un gel contenant également 100 ppm de composé  given by way of illustration but not limitation. The appended drawing comprises a single figure showing battery discharge curves of the prior art and a battery according to the invention. A mercury-free, cadmium-free and lead-free alkaline battery A is prepared, the negative electrode of which consists of virgin zinc powder dispersed in a gel which also contains 100 ppm of compound.

de stabilisation C6F13C2H4 (C 2H4 0) OH.  stabilizer C6F13C2H4 (C 2H4 O) OH.

6 13 24 2 4 146 13 24 2 4 14

On étudie tout d'abord la vitesse de corrosion de cette électrode au contact de l'électrolyte alcalin. Cette vitesse est évaluée par le volume d'hydrogène formé en microlitre (F1) par gramme d'alliage de zinc (g) par jour (j) en opérant à 60 C.- (Ainsi, à titre de référence, une pile de l'art antérieur dont le zinc est amalgammé à 5 % présente une vitesse de corrosion de 1,5 %l/g/jour environ, cette valeur étant acceptable dans la plupart des cas). La vitesse de corrosion de la pile  The corrosion rate of this electrode in contact with the alkaline electrolyte is first studied. This rate is evaluated by the volume of hydrogen formed in microliter (F1) per gram of zinc alloy (g) per day (j) operating at 60 ° C. (Thus, for reference, a battery of prior art whose zinc is amalgamated to 5% has a corrosion rate of about 1.5% l / g / day, this value being acceptable in most cases). The rate of corrosion of the battery

A est voisine de 1 Bl/gj, ce qui est tout à fait satisfaisant.  A is close to 1 Bgl / g, which is quite satisfactory.

On décharge ensuite cette pile, dans des conditions sévères, c'est-à-dire sur une résistance de 5 ohms. La figure 1 montre cette courbe de décharge A (ordonnées V en volts et abscisses h en heures). On  This battery is then discharged under severe conditions, that is to say on a resistance of 5 ohms. Figure 1 shows this discharge curve A (ordinate V in volts and abscissa h in hours). We

observe l'apparition d'un creux de 60 mvolts au bout d'une heure.  observe the appearance of a depression of 60 mvolts after one hour.

On prépare ensuite une pile alcaline B de l'art antérieur sans composé organique de stabilisation, mais dont le gel comporte de l'indium dans une proportion de 0,2 % du poids de zinc. La vitesse de corrosion de cette pile B est de 30 gl/gj, ce qui est tout à fait excessif pour une bonne conservation de la pile. La courbe de B de  An alkaline battery B of the prior art is then prepared without an organic stabilizing compound, but the gel of which contains indium in a proportion of 0.2% by weight of zinc. The rate of corrosion of this battery B is 30 gl / g, which is quite excessive for good conservation of the battery. The curve of B of

décharge est correcte.discharge is correct.

On prépare ensuite une pile C selon l'invention dont l'électrode de  Next, a cell C according to the invention is prepared, the electrode of which

zinc contient 50 ppm de C6F13C2H4 (C2H40)14 OH et 0,2 % d'indium.  zinc contains 50 ppm C6F13C2H4 (C2H40) 14 OH and 0.2% indium.

- Dans un mélangeur, sont introduits une solution d'électrolyte alcalin, qui est une solution de potasse saturée d'oxyde dezinc, et le gélifiant qui est de la carboxyméthylcellulose; pendant la rotation du mélangeur, on introduit la poudre de zinc puis une solution de chlorure d'indium concentré et le composé organique de stabilisation. Après homogénéisation pendant quelques minutes, le gel anodique est prêt et  In a mixer, there is introduced an alkaline electrolyte solution, which is a solution of potassium hydroxide saturated with zinc oxide, and the gelling agent which is carboxymethylcellulose; during the rotation of the mixer, the zinc powder is introduced and then a solution of concentrated indium chloride and the organic stabilization compound. After homogenization for a few minutes, the anodic gel is ready and

peut être stocké plusieurs jours avant d'être utilisé.  can be stored several days before being used.

En ce qui concerne la vitesse de corrosion du zinc de la pile C, il est tout à fait surprenant de constater que, malgré la diminution de la teneur en composé de stabilisation par rapport à la pile A, la vitesse de corrosion de la pile C est de iI/gj, alors qu'elle était de 30 #l/gj  With regard to the zinc corrosion rate of cell C, it is quite surprising that, despite the decrease in stabilization compound content relative to cell A, the corrosion rate of cell C is iI / gj, whereas it was 30 # l / gj

dans la pile B contenant le même pourcentage d'indium.  in cell B containing the same percentage of indium.

La couche de décharge C montre une amélioration très sensible de la décharge et la disparition du creux de tension au bout d une heure. Il y a donc une régularisation de la capacité à régime dur avec tension de  The discharge layer C shows a very significant improvement in the discharge and the disappearance of the voltage dip after one hour. There is therefore a regularization of the capacity with hard regime with tension of

coupure élevée.high cut.

On prépare enfin une pile D selon l'invention du même genre que la pile C, mais avec des teneurs beaucoup plus faibles en indium et en  Finally, a battery D according to the invention of the same kind as cell C is prepared, but with much lower levels of indium and

composé de stabilisation: 0,05 % d'indium et 10 ppm de composé.  stabilizing compound: 0.05% indium and 10 ppm compound.

La vitesse de corrosion n'est que de 3Ul/gj, et la courbe de  The corrosion rate is only 3Ul / gd, and the

décharge D est tout à fait normale.  D discharge is quite normal.

Il existe donc un effet de combinaison tout à fait surprenant des  There is therefore a quite surprising combination effect of

deux ajouts même en très faible quantité.  two additions even in very small quantities.

Dans d'autres variantes de réalisation de piles selon l'invention à bonnes courbes d-_ d--zha-ge, c- cSnslace que lorsque la poudre de zinc est traitée par 0,03 % d'indium, avec un ajout de 10C ppm de composé de stabilisation, la vitesse de corrosion est de 1 à 2 uiL/gj, alors qu'elle  In other alternative embodiments of batteries according to the invention with good d-zha-ge curves, it is important that when the zinc powder is treated with 0.03% of indium, with an addition of 10C ppm stabilizing compound, the corrosion rate is 1 to 2 uiL / gj, while

est de 100 xl/gj avec seulement 0,03 % d'indium.  is 100 xl / gd with only 0.03% indium.

Bien entendu l'invention n'est pas limitée aux modes de réalisation décrits ci-dessus. Le composé organique C6F13C2H4 (C2H40) 14 OH peut être  Naturally, the invention is not limited to the embodiments described above. The organic compound C6F13C2H4 (C2H40) 14 OH can be

remplacé par l'un des composés répertoriés plus haut.  replaced by one of the compounds listed above.

De même, pour réaliser l'électrode de zinc, on peut remplacer l'utilisation de chlorure d'indium par l'introduction de-l'indium dans  Similarly, to achieve the zinc electrode, the use of indium chloride can be replaced by the introduction of indium into

un alliage en poudre zinc-indium.a zinc-indium powder alloy.

Les composés organiques précités, et notamment celui qui a été pris comme exemple, sont caractérisés par leur innocuité; leur présence peut être mise en évidence par leur spectre RMN (Relaxation Magnétique Nucléaire) 7-  The aforementioned organic compounds, and especially that which has been taken as an example, are characterized by their innocuousness; their presence can be demonstrated by their NMR (Nuclear Magnetic Relaxation) spectrum.

Claims (7)

REVENDICATIONS 1/ Générateur électrochimique à électrolyte alcalin et à électrode négative de zinc, caractérisé par le fait que ladite électrode de zinc exempte de mercure, de cadmium et de plomb, contient 0,005 % à 1 % en poids d'indium et 1 à 1000 ppm d'au moins un composé organique de stabilisation choisi parmi les composés polyfluorés du type fluoroalcool éthoxylé et les composés du type sulfure d'alcoyle et d'alcool polyéthoxylé. 2/ Générateur électrochimique selon la revendication 1, caractérisé par le fait que la teneur dudit composé organique est comprise entre 10 et ppm.  1 / Electrochemical generator with alkaline electrolyte and negative zinc electrode, characterized in that said zinc electrode free of mercury, cadmium and lead, contains 0.005% to 1% by weight of indium and 1 to 1000 ppm of at least one organic stabilizing compound chosen from polyfluoro compounds of the ethoxylated fluoroalcohol type and compounds of the alkyl sulphide and polyethoxylated alcohol type. 2 / Electrochemical generator according to claim 1, characterized in that the content of said organic compound is between 10 and ppm. 3/ Générateur électrochimique selon l'une des revendications 1 et 2,  3 / Electrochemical generator according to one of claims 1 and 2, caractérisé par le fait que la teneur en indium est comprise entre 0,03  characterized in that the indium content is between 0.03 % et 0,2 % par rapport au poids du métal.  % and 0.2% relative to the weight of the metal. 4/ Générateur électrochimique selon la revendication l, caractérisé par  4 / Electrochemical generator according to claim 1, characterized by le fait qu'il contient 0,03 % d'indium et 50 ppm de composé organique.  the fact that it contains 0.03% indium and 50 ppm organic compound. / Générateur électrochimique selon la revendication 1, caractérisé par  Electrochemical generator according to claim 1, characterized by le fait qu'il contient 0,2 % d'indium et 100 ppm de composé organique.  the fact that it contains 0.2% indium and 100 ppm organic compound. 6/ Générateur électrochimique selon la revendication 1, caractérisé par  6 / Electrochemical generator according to claim 1, characterized by le fait qu'il contient 0,1 % d'indium et 10 ppm de composé organique.  the fact that it contains 0.1% indium and 10 ppm organic compound. 7/ Générateur électrochimique selon la revendication 1, caractérisé par  7 / Electrochemical generator according to claim 1, characterized by le fait qu'il contient 0,05 % d'indium et 10 ppm de composé organique.  the fact that it contains 0.05% indium and 10 ppm organic compound. 8/,Générateur électrochimique selon l'une des revendications  8 /, electrochemical generator according to one of the claims précédentes, caractérisé par le fait que ledit composé organique répond à la formule (1) CnF2n+, - (CH2)p - (CH2CH20)q - OH dans laquelle: n est compris entre 4 et 20, de préférence entre 6 et 8, p est compris entre 1 et 10 et de préférence voisin de 2, et  preceding, characterized in that said organic compound corresponds to the formula (1) CnF2n +, - (CH2) p - (CH2CH2O) q - OH in which: n is between 4 and 20, preferably between 6 and 8, p is between 1 and 10 and preferably close to 2, and q est compris entre 3 et 40, de préférence entre 10 et 12.  q is between 3 and 40, preferably between 10 and 12. 9/ Générateur électrochimique selon la revendication 8, caractérisé par le fait que ledit composé organique répond à la formule  9 / Electrochemical generator according to claim 8, characterized in that said organic compound corresponds to the formula C6 F13 C2 H4 (C2H40) OH dans laquelle q est voisin de 12.  C6 F13 C2 H4 (C2H40) OH in which q is close to 12. F 3 2 4 q / Générateur électrochimique selon la revendication 1, caractérisé par le fait que ladite électrode de zinc contient en mélange:  F 3 2 4 q / Electrochemical generator according to claim 1, characterized in that said zinc electrode contains in mixture: C F13 C H (C2H40)1 OHC F13 C H (C2H40) 1H 6 13 2 4 2 4 146 13 2 4 2 4 14 aTJTWe.;sa H IoTePeU ZTPaI anb zTuj al aed gSTJaZseaMZ 't7T UTOtIMOTPUAaeG 21 UOCaS fnbTLUTtDOJDD819 jn;Iau9u /91  aTJTWe., his ZTPaI HoTePeU anb zTuj al aed gSTJaZseaMZ 't7T UTOtIMOTPUAaeG 21 UOCaS fnbTLUTtDOJDD819 jn; Iau9u / 91 -'oz UoCTAUe aa z 9JUa STadWOO Zsa u -  UoCTAUe aa z 9JUa STadWOO Zsa u - no/za 'auoqae ap sauo; El uoJTAU@ e aGTLoo leoTpeM un;sa H -  no / za 'auoqae ap sauo; El uoJTAU @ e aGTLoo leoTpeM a; his H - : anb rTes al aed SZ 9STI:JGDOeB D 'E uoDieCTpuaaJ 'el uolas anbtTooT olJ GTG naapeue9 /7I  : anb rtes al aed SZ 9STI: JGDOeB of E uoDieCTpuaaJ 'el uolas anbtTooT olJ GTG naapeue9 / 7I DOT a z aua sTdUoo;sa u -DOT a z aua sTdUoo; Za 'aeúlú ool!eoTpeJ unZa 'aeúlú ool! EoTpeJ a no a@úle TeoTpeT un 'GTJ:TeW uou no a7T:eaJ 'alXooTM ILeTPea un zsa H -  no TeoTpeT a GTJ: TeW ouou no a7T: eaJ 'alXooTM ILeTPea a zsa H - : allanbel suep alnaio; CE H i- '- HD-HD-O, - HD) -S-H !' a7ln-oj el E puodga -b:urejo asoduoo;Tpaj anb;Tmj al ed gsT;aoeD 'I uOeDoTpuaAaU ie uo7as anbT7.TqooZoaG? Inazeguao /Et  : allanbel suep alnaio; This is HD-HD-O, HD) -S-H! a7ln-oj el E puodga -b: urejo asoduoo; Tpaj anb; tmj al ed gsT; aoeD 'I uOeDoTpuaAaU ie uo7as anbT7.TqooZoaG? Inazeguao / And ú 9Eú 9E HO - "O H HO) - () ' S= - S D THO - "HO HO) - () 'S = - S D T iD iTD (e n JOnuJ o; l e puodai @rb:ue2Io esodwoD tTpaT anb zT; av JxBd GSTUGJZeJeD ', UOT;eUTpuaAai eT uolas anbTt4ooI0;@alq anaZtea9u9D /ZT -ET -,aOT a Gl Ue Gouaa;,ad ap 'O^ @a ú aa.ua sT.dudo;@s b Z ap UTsTOA oueagj9gad ap z.a 01; a I a..iua sTudwoD qsa d 01 8 qa 9 aj:.ua aouaaegad ap 'OZ za 7 ai ua sTaduoo:.se u : alanbml suep b EdE-U U H0 O HODzHO) _ d(EH) - i-uFt u (E) alnwaog ew e puodgai anbTueJo gsodwoo;TpaT anb 7e$ al Jed asTC 'I UOTOzTpuaAaa el uotas anbTq0DootoaGI fnale gauGD /JT S HO I(0oHD) HO D I OD : asodwoo ne zuepuodsaioo auuaúow axTeTnzaTow assew aun DaAe t71 107HE 17E TE OT H0 (0 z) HO i 3 -99- na  iD iTD (in JOnuJ o; the puodai @rb: ue2Io esodwoD tTpaT anb zT; av JxBd GSTUGJZeJeD ', UOT; eUTpuaAai and uolas anbTt4ooI0; @alq anaZtea9u9D / ZT -ET -, aOT a Gl Ue Gouaa;, ad ap' O @ a..................................................... u: alanbml suep b EdE-U U H0 O HODzHO) _ d (EH) - i-uFt u (E) alnwaog ew e puodgai anbTueJo gsodwoo; TpaT anb 7e $ al Jed asTC 'I UOTOzTpuaAaa el uotas anbTq0DootoaGI fnale gauGD / JT S HO I (0oHD) HO DI OD: asodwoo ne zuepuodsaioo auuaúow axTeTnzaTow assew aun DaAe t71 107HE 17E TE OT H0 (0 z) HO i 3 -99- na
FR8810013A 1988-07-25 1988-07-25 ELECTROCHEMICAL GENERATOR WITH ALKALINE ELECTROLYTE AND ZINC NEGATIVE ELECTRODE Expired - Fee Related FR2634594B1 (en)

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FR8810013A FR2634594B1 (en) 1988-07-25 1988-07-25 ELECTROCHEMICAL GENERATOR WITH ALKALINE ELECTROLYTE AND ZINC NEGATIVE ELECTRODE
CH2387/89A CH679713A5 (en) 1988-07-25 1989-06-27
DE3923751A DE3923751C2 (en) 1988-07-25 1989-07-18 Electrochemical generator with an alkaline electrolyte and a negative zinc electrode and process for its production
JP1192421A JPH0279367A (en) 1988-07-25 1989-07-25 Electrochemical battery equipped with alkaline electrolyte and zinc negative electrode

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FR8810013A FR2634594B1 (en) 1988-07-25 1988-07-25 ELECTROCHEMICAL GENERATOR WITH ALKALINE ELECTROLYTE AND ZINC NEGATIVE ELECTRODE

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EP0474382A1 (en) * 1990-08-14 1992-03-11 Eveready Battery Company, Inc. Substantially mercury-free electrochemical cells
US5198315A (en) * 1991-03-12 1993-03-30 Sanyo-Ekuseru Kabushikigaisha Zinc alkaline cells
US5209995A (en) * 1991-03-12 1993-05-11 Sanyo-Denki Kabushikigaisha Zinc alkaline cells
EP0558003A1 (en) * 1992-02-26 1993-09-01 Matsushita Electric Industrial Co., Ltd. Method of manufacturing zinc-alkaline batteries
EP0582293A2 (en) * 1992-08-04 1994-02-09 Seiko Instruments Inc. Alkaline battery, production method of alkaline battery, and applied product using alkaline battery
WO1995031011A1 (en) * 1994-05-06 1995-11-16 Battery Technologies Inc. Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture
FR2734408A1 (en) * 1995-05-19 1996-11-22 Europ Accumulateurs A process for the redn. of residual charge current in a gas re-combination accumulator
US6221530B1 (en) 1996-12-23 2001-04-24 Aer Energy Resources, Inc. Mercury-free zinc anode for electromechanical cell and method for making same
US6602629B1 (en) 2000-05-24 2003-08-05 Eveready Battery Company, Inc. Zero mercury air cell

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JPH0732015B2 (en) * 1989-04-07 1995-04-10 松下電器産業株式会社 Alkaline battery
US5168018A (en) * 1990-05-17 1992-12-01 Matsushita Electric Industrial Co., Ltd. Method of manufacturing zinc-alkaline batteries
JPH0738306B2 (en) * 1991-04-22 1995-04-26 松下電器産業株式会社 Zinc alkaline battery
JPH0785877A (en) * 1993-09-10 1995-03-31 Toshiba Battery Co Ltd Button type alkaline battery
ES2229956B2 (en) * 2004-10-26 2006-12-01 Celaya Emparanza Y Galdos, S.A. (Cegasa) AN ELECCHEMICAL ELEMENT AND METHODOLOGY FOR THE SELECTION OF SOME OF ITS COMPONENTS.

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Cited By (17)

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Publication number Priority date Publication date Assignee Title
US5464709A (en) * 1990-08-14 1995-11-07 Eveready Battery Company, Inc. Alkaline cells that are substantially free of mercury
EP0845827A3 (en) * 1990-08-14 2002-06-19 Eveready Battery Company, Inc. Substantially mercury-free electrochemical cells
EP0845827A2 (en) * 1990-08-14 1998-06-03 Eveready Battery Company, Inc. Substantially mercury-free electrochemical cells
EP0474382A1 (en) * 1990-08-14 1992-03-11 Eveready Battery Company, Inc. Substantially mercury-free electrochemical cells
US5364715A (en) * 1990-08-14 1994-11-15 Eveready Battery Company, Inc. Alkaline cells that are substantially free of mercury
US5198315A (en) * 1991-03-12 1993-03-30 Sanyo-Ekuseru Kabushikigaisha Zinc alkaline cells
US5209995A (en) * 1991-03-12 1993-05-11 Sanyo-Denki Kabushikigaisha Zinc alkaline cells
EP0558003A1 (en) * 1992-02-26 1993-09-01 Matsushita Electric Industrial Co., Ltd. Method of manufacturing zinc-alkaline batteries
US5308374A (en) * 1992-02-26 1994-05-03 Matsushita Electric Industrial Co., Ltd. Method of manufacturing zinc-alkaline batteries
EP0582293A3 (en) * 1992-08-04 1996-08-14 Seiko Instr Inc Alkaline battery, production method of alkaline battery, and applied product using alkaline battery
US6723469B1 (en) 1992-08-04 2004-04-20 Siixmicro Parts Ltd. Alkaline battery without mercury and electronic apparatus powered thereby
EP0582293A2 (en) * 1992-08-04 1994-02-09 Seiko Instruments Inc. Alkaline battery, production method of alkaline battery, and applied product using alkaline battery
US6586139B1 (en) 1992-08-04 2003-07-01 Seiko Instruments Inc. Alkaline battery without mercury and electronic apparatus powered thereby
WO1995031011A1 (en) * 1994-05-06 1995-11-16 Battery Technologies Inc. Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture
FR2734408A1 (en) * 1995-05-19 1996-11-22 Europ Accumulateurs A process for the redn. of residual charge current in a gas re-combination accumulator
US6221530B1 (en) 1996-12-23 2001-04-24 Aer Energy Resources, Inc. Mercury-free zinc anode for electromechanical cell and method for making same
US6602629B1 (en) 2000-05-24 2003-08-05 Eveready Battery Company, Inc. Zero mercury air cell

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DE3923751C2 (en) 1999-05-20
JPH0279367A (en) 1990-03-19
FR2634594B1 (en) 1993-06-18
DE3923751A1 (en) 1990-02-08
CH679713A5 (en) 1992-03-31

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