DE1096986B - Use of a negative cadmium electrode in alkaline batteries that are permanently sealed gas-tight or that work without visible gas evolution - Google Patents

Use of a negative cadmium electrode in alkaline batteries that are permanently sealed gas-tight or that work without visible gas evolution

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Publication number
DE1096986B
DE1096986B DEA32732A DEA0032732A DE1096986B DE 1096986 B DE1096986 B DE 1096986B DE A32732 A DEA32732 A DE A32732A DE A0032732 A DEA0032732 A DE A0032732A DE 1096986 B DE1096986 B DE 1096986B
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DE
Germany
Prior art keywords
electrode
zinc
negative electrode
gas
negative
Prior art date
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.)
Pending
Application number
DEA32732A
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German (de)
Inventor
Dr Hans Bode
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.)
Accumulatoren Fabrik AG
Original Assignee
Accumulatoren Fabrik AG
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 Accumulatoren Fabrik AG filed Critical Accumulatoren Fabrik AG
Priority to DEA32732A priority Critical patent/DE1096986B/en
Publication of DE1096986B publication Critical patent/DE1096986B/en
Priority claimed from US334043A external-priority patent/US3208880A/en
Pending legal-status Critical Current

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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • 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
    • 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
    • H01M4/44—Alloys based on cadmium
    • 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)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

DEUTSCHESGERMAN

Die Erfindung betrifft die Herstellung einer Entladereserve der negativen Elektrode bei dauernd gasdicht verschlossenen oder ohne sichtbare Gasentwicklung arbeitenden alkalischen Akkumulatoren durch Verwendung einer negativen Cadmium-Elektrode, die einen Zusatz von metallischem Zink enthält.The invention relates to the production of a discharge reserve of the negative electrode while being permanently gas-tight alkaline accumulators that are closed or that work without any visible evolution of gas Use of a negative cadmium electrode that contains metallic zinc.

Der Zusatz von metallischem Zink zu den negativen Elektroden alkalischer Akkumulatoren, die offen betrieben werden, ist bekannt. Es ist auch bereits bekannt, gasdicht verschlossene Akkumulatoren so aufzuladen, daß die negative Elektrode im Augenblick des gasdichten Verschließen höher aufgeladen ist als die positive Elektrode, d. h. eine Entladereserve besitzt. Die Entladereserve der negativen Elektrode besteht bei dieser bekannten Ausführungsform aus einem Überschuß an metallischem Cadmium und/oder aus metallischem Kupfer.The addition of metallic zinc to the negative electrodes of alkaline batteries that operate openly is known. It is also already known to charge gas-tight sealed accumulators in such a way that that the negative electrode is charged higher than at the moment of gas-tight sealing the positive electrode, d. H. has a discharge reserve. The discharge reserve of the negative electrode exists in this known embodiment from an excess of metallic cadmium and / or from metallic copper.

Ein wesentlicher Nachteil dieses bekannten Vorschlages besteht darin, daß durch die Verwendung des verhältnismäßig edlen Kupfers das Potential nach Verbrauch des Cadmiums stark abfällt und die weitere Entladung bei einem weit niedrigeren Potential verläuft.A major disadvantage of this known proposal is that by using the relatively noble copper the potential drops sharply after consumption of the cadmium and the further Discharge proceeds at a far lower potential.

Aufgabe der vorliegenden Erfindung war es, ein Verfahren zur Erzeugung einer Entladereserve der negativen Elektrode eines dauernd gasdicht verschlossenen oder ohne sichtbare Gasentwicklung arbeitenden alkalischen Akkumulators zu schaffen, bei dem dieser Potentialabfall am Ende der Entladung nicht auftritt und die Potentiallage der negativen Elektrode während der ganzen Entladung möglichst hoch ist.The object of the present invention was to provide a method for generating a discharge reserve negative electrode of a permanently sealed gas-tight or working without visible gas development to create alkaline accumulator, in which this potential drop does not occur at the end of the discharge and the potential of the negative electrode is as high as possible during the entire discharge.

Diese Aufgabe wurde durch die Verwendung einer negativen Cadmium-Elektrode, die einen Zusatz von metallischem Zink enthält, gelöst.This task was accomplished through the use of a negative cadmium electrode that had an addition of contains metallic zinc, dissolved.

Das Zink kann der aktiven Masse der negativen Elektrode z. B. in Form von Pulver oder von Spänen zugemischt werden.The zinc can be added to the active mass of the negative electrode e.g. B. in the form of powder or chips are mixed in.

Es ist auch möglich, der Elektrode an Stelle von Zink auch eine Zink-Cadmium-Legierung in irgendeiner beliebigen Form zuzusetzen.It is also possible to use a zinc-cadmium alloy in any of the electrodes instead of zinc add any shape.

In einer weiteren Ausführungsform der Erfindung kann das Zink in der negativen Elektrode auch in besonderen Elektrodenteilen oder von der Elektrode räumlich getrennt, jedoch elektrisch leitend mit ihr verbunden, untergebracht werden, wobei es in diesem Falle z. B. in Form von Blech oder in Stabform verwendet werden kann. Eine bevorzugte Ausführungsform der Erfindung besteht darin, daß das metallische Zink zur negativen Elektrode in Granulatform zugesetzt wird. Auf diese Weise wird eine leichte Dosierung des Zusatzes ermöglicht und gleichzeitig eine gute Vermischung mit der Cadmiummasse erzielt.In a further embodiment of the invention, the zinc in the negative electrode can also in particular Electrode parts or spatially separated from the electrode, but electrically conductive with her connected, are accommodated, in this case, for. B. used in the form of sheet metal or in rod form can be. A preferred embodiment of the invention is that the metallic Zinc is added to the negative electrode in granular form. This way it becomes a light dosage of the additive and at the same time achieved good mixing with the cadmium mass.

Es besteht auch die Möglichkeit, das Zink auf der negativen Elektrode elektrolytisch abzuscheiden. Die-Verwendung It is also possible to electrolytically deposit the zinc on the negative electrode. The usage

einer negativen Cadmium-Elektrode in dauernd gasdicht verschlossenen oder ohne sichtbare Gasentwicklunga negative cadmium electrode in a permanently sealed gas-tight or without visible gas evolution

arbeitenden alkalischen Akkumulatorenworking alkaline batteries

Anmelder:Applicant:

Accumulatoren-Fabrik Aktiengesellschaft, Hagen (Westf.), Dieckstr.42Accumulatoren-Fabrik Aktiengesellschaft, Hagen (Westphalia), Dieckstrasse 42

Dr. Hans Bode, Frankfurt/M., ist als Erfinder genannt wordenDr. Hans Bode, Frankfurt / M., Has been named as the inventor

ses Verfahren ist vorzugsweise bei Sinterelektroden anzuwenden, bei denen das gegen den Elektrolyt beständige Gerüst beispielsweise mit der Lösung eines Cadmium- oder eines Zinksalzes getränkt wird, wonach das Zink zusammen mit dem Cadmium auf elektrolytischem Wege abgeschieden werden kann.This method is preferably to be used with sintered electrodes, which are resistant to the electrolyte The framework is soaked, for example, with a solution of a cadmium or a zinc salt, after which the zinc can be deposited electrolytically together with the cadmium.

Es besteht auch die Möglichkeit, das Zink aus einer Salzlösung auf chemischem Wege in Form des Hydroxydes abzuscheiden und dieses Hydroxyd dann elektrochemisch zu Metall zu reduzieren.There is also the possibility of the zinc from a salt solution by chemical means in the form of To deposit hydroxide and then electrochemically reduce this hydroxide to metal.

Schließlich kann das Zink durch Auszementieren aus einer Zinksalzlösung mittels eines unedlen Metalls, z. B. von Magnesium oder Aluminium, abgeschieden werden.Finally, the zinc can be cemented out of a zinc salt solution using a base metal, z. B. of magnesium or aluminum, are deposited.

Es hat sich als besonders zweckmäßig erwiesen, den Zinkzusatz auf 10 bis 50%, vorzugsweise etwa 20% der Kapazität, gemessen in Amperestunden der aktiven Masse der negativen Elektrode, zu bemessen.It has proven to be particularly useful to add 10 to 50% zinc, preferably about 20% the capacity, measured in ampere-hours of the active mass of the negative electrode.

Besonders vorteilhaft ist es, die Entladereserve der negativen Elektrode durch Zusatz von Zink zu erzeugen, wenn die positive Elektrode des gasdicht verschlossenen oder ohne sichtbare Gasentwicklung arbeitenden Akkumulators sogenannte antipolare Masse enthält, d. h. die Masse, die normalerweise in der negativen Elektrode als aktive Masse verwendet wird, beispielsweise Cadmiummasse. In diesem Falle hat die Entladereserve der negativen Elektrode den Vorteil, daß bei Tiefentladung die antipolare Masse in der positiven Elektrode, die als Oxyd oder Hydroxyd des Cadmiums vorliegt, bereits vor Beginn der Sauerstoff-It is particularly advantageous to generate the discharge reserve of the negative electrode by adding zinc, if the positive electrode of the gas-tight sealed or working without visible gas evolution Accumulator contains so-called antipolar mass, d. H. the crowd normally found in the negative electrode is used as the active mass, for example cadmium mass. In this case the Discharge reserve of the negative electrode has the advantage that the antipolar mass in the positive electrode, which is present as an oxide or hydroxide of cadmium, even before the start of the oxygen

009 698/134009 698/134

entwicklung in der negativen Elektrode zum Teil zu Cadmium reduziert wird, wodurch ein Sauerstoffverzehr ermöglicht wird, sobald sich an der negativen Elektrode Sauerstoff entwickelt.Development in the negative electrode is partially reduced to cadmium, which leads to oxygen consumption is made possible as soon as oxygen develops at the negative electrode.

Claims (7)

Patentansprüche:Patent claims: 1. Verwendung einer negativen Cadmium-Elektrode, die einen Zusatz von metallischem Zink enthält, in dauernd gasdicht verschlossenen oder ohne sichtbare Gasentwicklung arbeitenden alkalischen Akkumulatoren.1. Using a negative cadmium electrode, which contains an addition of metallic zinc, in permanently gas-tight sealed or without visible evolution of gas from working alkaline accumulators. 2. Elektrode nach Anspruch 1, dadurch gekennzeichnet, daß in bekannter Weise das Zink der aktiven Masse der negativen Elektrode zugemischt ist.2. Electrode according to claim 1, characterized in that the zinc in a known manner active mass of the negative electrode is mixed. 3. Elektrode nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß das Zink der negativen Elektrode in Form einer Zink-Cadmium-Legierung zugesetzt ist.3. Electrode according to claims 1 and 2, characterized in that the zinc is the negative Electrode in the form of a zinc-cadmium alloy is added. 4. Elektrode nach Anspruch 1, dadurch gekennzeichnet, daß das Zink in der negativen Elektrode in besonderen Elektrodenteilen oder von der Elektrode räumlich getrennt, jedoch elektrisch leitend mit ihr verbunden, untergebracht ist.4. Electrode according to claim 1, characterized in that the zinc in the negative electrode in special electrode parts or spatially separated from the electrode, but electrically conductive connected to it, is housed. 5. Elektrode nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß das metallische Zink zur negativen Elektrode in Granulatform zugesetzt ist.5. Electrode according to claims 1 to 4, characterized in that the metallic zinc for negative electrode is added in granular form. 6. Elektrode nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß das Zink auf der negativen Elektrode elektrolytisch abgeschieden ist.6. Electrode according to claims 1 to 4, characterized in that the zinc on the negative Electrode is deposited electrolytically. 7. Elektrode nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß der Zinkzusatz 10 bis 5Oe/o, vorzugsweise etwa 2OVo, der Kapazität der aktiven Masse der negativen Elektrode beträgt.7. Electrode according to claims 1 to 6, characterized in that the zinc additive is 10 to 50 e / o, preferably about 20 o, the capacity of the active mass of the negative electrode. In Betracht gezogene Druckschriften:
Französische Patentschrift Nr. 1 025 843;
britische Patentschriften Nr. 794592, 780481.Considered publications:
French Patent No. 1,025,843;
British Patent Nos. 794592, 780481. © 009 698/134 1.61© 009 698/134 1.61
DEA32732A 1959-08-26 1959-08-26 Use of a negative cadmium electrode in alkaline batteries that are permanently sealed gas-tight or that work without visible gas evolution Pending DE1096986B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEA32732A DE1096986B (en) 1959-08-26 1959-08-26 Use of a negative cadmium electrode in alkaline batteries that are permanently sealed gas-tight or that work without visible gas evolution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEA32732A DE1096986B (en) 1959-08-26 1959-08-26 Use of a negative cadmium electrode in alkaline batteries that are permanently sealed gas-tight or that work without visible gas evolution
US334043A US3208880A (en) 1963-12-27 1963-12-27 Alkaline storage battery and process for making the same

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Publication Number Publication Date
DE1096986B true DE1096986B (en) 1961-01-12

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DEA32732A Pending DE1096986B (en) 1959-08-26 1959-08-26 Use of a negative cadmium electrode in alkaline batteries that are permanently sealed gas-tight or that work without visible gas evolution

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2468216A1 (en) * 1979-10-24 1981-04-30 Anvar Alkaline accumulator using zinc:cadmium alloy as negative electrode - esp. where electrolyte is potassium hydroxide soln., and second electrode is nickel

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1025843A (en) * 1949-10-12 1953-04-20 Svenska Ackumulator Ab Improvements to electric accumulators
GB780481A (en) * 1951-09-08 1957-08-07 Accumulatoren Fabrik Ag Improvements in or relating to the manufacture of negative electrodes for alkaline accumulators
GB794592A (en) * 1954-08-17 1958-05-07 Svenska Ackumulator Ab Improvements in or relating to electric cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1025843A (en) * 1949-10-12 1953-04-20 Svenska Ackumulator Ab Improvements to electric accumulators
GB780481A (en) * 1951-09-08 1957-08-07 Accumulatoren Fabrik Ag Improvements in or relating to the manufacture of negative electrodes for alkaline accumulators
GB794592A (en) * 1954-08-17 1958-05-07 Svenska Ackumulator Ab Improvements in or relating to electric cells

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2468216A1 (en) * 1979-10-24 1981-04-30 Anvar Alkaline accumulator using zinc:cadmium alloy as negative electrode - esp. where electrolyte is potassium hydroxide soln., and second electrode is nickel

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