DE899216C - Positive and negative electrodes for alkaline batteries - Google Patents

Positive and negative electrodes for alkaline batteries

Info

Publication number
DE899216C
DE899216C DEA14618A DEA0014618A DE899216C DE 899216 C DE899216 C DE 899216C DE A14618 A DEA14618 A DE A14618A DE A0014618 A DEA0014618 A DE A0014618A DE 899216 C DE899216 C DE 899216C
Authority
DE
Germany
Prior art keywords
regular
electrodes
hydroxide
hydrogen
mass
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.)
Expired
Application number
DEA14618A
Other languages
German (de)
Inventor
Dipl-Chem Dr Adolf Dassler
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
Priority to BE515722D priority Critical patent/BE515722A/xx
Priority to NL88619D priority patent/NL88619C/xx
Application filed by Accumulatoren Fabrik AG filed Critical Accumulatoren Fabrik AG
Priority to DEA14618A priority patent/DE899216C/en
Priority to AT181300D priority patent/AT181300B/en
Priority to CH314756D priority patent/CH314756A/en
Priority to FR1066769D priority patent/FR1066769A/en
Priority to GB30287/52A priority patent/GB784851A/en
Application granted granted Critical
Publication of DE899216C publication Critical patent/DE899216C/en
Expired legal-status Critical Current

Links

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
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0497—Chemical precipitation
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/76—Containers for holding the active material, e.g. tubes, capsules
    • H01M4/765—Tubular type or pencil type electrodes; tubular or multitubular sheaths or covers of insulating material for said tubular-type electrodes
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

Nadh längerer Benutzung im praktischen Betrieb haben die einzelnen Zellen alkalischer Akkumulatorenbatterien erfahrungsgemäß nicht immer eine untereinander gleichmäßige Kapazität, und zwar auch dann nicht, wenn sie bei ihrer Anfertigung mit gleichen Mengen aktiven Materials gleicher Beschaffenheit ausgerüstet wurden. Trotz gleicher elektrischer Behandlung unterliegen die in Serie geschalteten Einzelzellen der Batterie im Laufe der Zeit verschieden raschem Verschleiß. Bei Entladung der Batterie fällt dann die Klemmenspannung einiger Elemente vorzeitig ab, während die anderen noch genügend Klemmenspannung besitzen,, um eine weitere Stromentnahme aus der Batterie zu gestatten. Die Verschiedenheit in der Kapazität der Einzelzellen kann schließlich, besonders bei mangelhafter Wartung, so groß werden, daß einige Zellen bei erschöpfender Entladung der Batterie ihre Polarität umkehren. Bei weiter über diese Umpolung hinaus fließendem Entladestrom erfolgt dann an den Elektroden solcher Elemente bald, nachdem deren Klemmenspannung den Nullpunkt unterschritten und ihre Polarität gewechselt hat, eine dem Entladestrom entsprechende Entwicklung von Wasserstoff oder Sauerstoff bzw. von beiden Gasen zugleich, je nachdem sich die positiven oder negativen bzw. beide Elektroden zugleich umpolen.The individual cells of alkaline storage batteries have after prolonged use in practical operation experience has shown that they do not always have a uniform capacity, not even if they are used when they are made have been equipped with the same amounts of active material of the same nature. Despite the same The series-connected individual cells of the battery are subject to electrical treatment in the course of the Time of different rapid wear. When the battery is discharged, the terminal voltage drops of some elements prematurely, while the others still have enough terminal voltage, to allow further current draw from the battery. The diversity in the After all, the capacity of the individual cells can be so large, especially if they are not properly maintained some cells will reverse their polarity when the battery is exhausted. at The discharge current flowing further beyond this polarity reversal then takes place at the electrodes such elements soon after their terminal voltage has fallen below zero and their Has changed polarity, a development of hydrogen corresponding to the discharge current or Oxygen or both gases at the same time, depending on whether the positive or negative or reverse polarity of both electrodes at the same time.

Diese Gasentwicklung bedingt einerseits, wenn Wasserstoff oder Knallgas entsteht, die Gefahr einer Explosion des Batteriebehälters, andererseits können die Behälter gasdicht verschlossener Elemente durch die entstehenden Gase aufgebläht und gesprengt werden. Dies ist auch bei Elementen zu befürchten, die z. B. gemäß Patentschrift 602· 702 gasabsorbierende Elektroden besitzen, da diese letzteren nur den geringen bei der Nachgasung nach der Ladung entstehenden Gasmengen ge-On the one hand, this gas development causes the danger if hydrogen or oxyhydrogen gas is produced an explosion of the battery container, on the other hand, the container can be gas-tight sealed elements are inflated and blown up by the gases produced. This is also the case with items fear the z. B. according to patent specification 602 · 702 have gas-absorbing electrodes, since these the latter only dealt with the small amounts of gas produced during post-gassing after the charge.

wachsen sind und außerdem im Falle ihrer Umpolung versagen·.are growing and also fail in the event of their polarity reversal ·.

Auf Grund der vorliegenden Erfindung ist ein Weg gefunden, um den Elektroden alkalischer Akkumulatoren die Eigentümlichkeit einer bei Weiterentladung über die Umpolung hinaus alsbald einsetzenden Gasentwicklung zu nehmen. Es wurde nach der Erfindung festgestellt, daß man die unmittelbar nach der Umpolung auftretendeBased on the present invention, a way has been found to make the electrodes more alkaline Accumulators have the peculiarity of an immediately upon further discharge beyond the polarity reversal the onset of gas evolution. It was found according to the invention that the occurring immediately after polarity reversal

ίο Wasserstoffentwicklung an der positiven Elektrode (Nickel-Oxyd-Elektrode) dadurch wirksam unterdrücken kann, daß man diese Elektrode nicht nur mit der gewöhnlich verwendeten regulären Masse (Nickelhydroxyd + Leitmaterial, z. B.ίο Development of hydrogen on the positive electrode (Nickel oxide electrode) can be effectively suppressed by using this electrode not only with the regular mass usually used (nickel hydroxide + conductive material, e.g.

Graphit oder Nickelflocken), sondern auch noch mit antipolarer Masse, d. h. hier in diesem Falle mit einem kathodisch reduzierbaren Oxyd, z. B. Cadmiumoxyd oder Cadmiumhydroxyd, füllt, also mit einem Material, wie es im alkalischen Akkumulator bisher vornehmlich1 zur Füllung der negativen Elektrode diente und welches bei einem unterhalb des. Abscheidungspotentials des Wasserstoffes liegenden Potentialwert reduzierbar ist. Das1 in der positiven Elektrode vorhandene Cadmiumoxyd wirfst dann gewissermaßen als Akzeptor für Wasserstoff, indem es bei Umpolung des Elementes bei einem wesentlich niedrigeren Potential reduziert wird, als es zur Entwicklung von Wasserstoff an der Elektrodte nötig ist. Erst nachdem das vorhandene Cadmiumoxyd zu Metall reduziert wurde, kann die Elektrode bei weiterem Stromdurchgang Wasserstoff entwickeln. Wenn man außerdem die Gegenelektrode, also die negative Elektrode des Elementes, genügend groß und leistungsfähig ausführt, d. h. mit dem nötigen Überschuß an negativer Masse versieht, kann ein derartiges Element bei vorübergehender Umpolung am Ende der Entladung keine Gase, weder Wasserstoff noch Sauerstoff, entwickeln.Graphite or nickel flakes), but also with antipolar mass, ie here in this case with a cathodically reducible oxide, e.g. B. cadmium oxide or cadmium hydroxide, filled, ie with a material such as that used in the alkaline storage battery 1 so far mainly for filling the negative electrode and which is reduced at a temperature below the. Deposition potential of the hydrogen potential value. The 1 existing in the positive electrode cadmium then throw a certain extent as an acceptor for hydrogen, by being reduced at polarity reversal of the element at a substantially lower potential than it is necessary for the development of hydrogen at the Elektrodte. Only after the existing cadmium oxide has been reduced to metal can the electrode develop hydrogen with further passage of current. If the counter electrode, i.e. the negative electrode of the element, is made sufficiently large and powerful, i.e. provided with the necessary excess of negative mass, such an element cannot develop any gases, neither hydrogen nor oxygen, if the polarity is temporarily reversed at the end of the discharge.

Man kann nach der Erfindung aber auch umgekehrt die positive Elektrode verstärken und die negative Elektrode mit antipolarer Masse ausrüsten, d. h, außer mit der regulären negativen Masse (Cadmium oder Eisen) noch mit einem anodisch oxydierbaren Oxyd, z.- B. Nickel-(2)-Hydroxyd, Kolbalt-(2)-Hydroxyd usw., oder auch mit einem anodisch oxydierbaren Metall, welches edler als das der regulären negativen Masse ist, z. B. mit Kupferpulver, füllen. In diesem Falle wirkt das in der Elektrode vorhandene Nickel-i(2)-Hydroxyd-oder das Kupfer als Akzeptor für den sonst bei Umpoking der Elektrode auftretenden Sauerstoff. Zur Verbesserung der Wirksamkeit der verwendeten antipolaren Masse setzt man dieser unter Umständen noch eine genügend große Menge Leitmaterial, z. B. Graphit oder Nickelnocken, zu.However, according to the invention, the positive electrode can also be strengthened and the reverse Equip negative electrode with antipolar mass, d. h, except with the regular negative Mass (cadmium or iron) with an anodically oxidizable oxide, e.g. nickel (2) hydroxide, Kolbalt- (2) -hydroxyd etc., or also with an anodically oxidizable metal, which is nobler than that of the regular negative mass, e.g. B. with copper powder. In this In the case, the nickel-i (2) -hydroxide or copper present in the electrode acts as an acceptor for the otherwise occurring when poking the electrode Oxygen. To improve the effectiveness of the used antipolar mass sets you may still have a sufficiently large amount of conductive material, z. B. graphite or Nickel cam, too.

Schließlich können nach der Erfindung beide Elektroden des Elementes außer mit regulären noch mit antipolaren Massen ausgerüstet werden, d. h. die positive Elektrode mit einem kathodisch reduzierbaren Oxyd, die negative Elektrode mit einem anodisch oxydierbaren Oxyd oder Metall, welches edler ist als das als reguläre Negative verwendete Metall und deshalb erst nach Entladung der regulären negativen Masse seine Wirksamkeit entfaltet.Finally, according to the invention, both electrodes of the element can be used except with regular electrodes be equipped with antipolar masses, d. H. the positive electrode with a cathodically reducible Oxide, the negative electrode with an anodically oxidizable oxide or metal, which is more noble than the metal used as a regular negative and therefore only after the regular negative has been discharged negative mass unfolds its effectiveness.

Die genannten antipolaren. Massen können nach der Erfindung entweder getrennt von den regulären Massen in besonderen Taschen, Röhrchen oder Platten oder Elementelektroden untergebracht oder auch mit den regulären Massen mehr oder weniger innig vermischt in die Elektroden eingefüllt werden. Auch kann man die reguläre Masse bzw. deren aktive Bestandteile gemeinsam mit den antipolaren Stoffen aus Lösungen ausfällen.The aforementioned antipolar. According to the invention, masses can either be separated from the regular Masses housed in special pockets, tubes or plates or element electrodes or also filled into the electrodes more or less intimately mixed with the regular masses will. You can also use the regular mass or its active ingredients together with the antipolar Precipitate substances from solutions.

Claims (1)

Patentansprüche:Patent claims: i. Positive bzw. negative Elektroden für alkalische Akkumulatoren, die bei weiter über ihre Umpolung hinaus fließendem Entladesfcrom keinen Wasserstoff (Sauerstoff) entwickeln, dadurch gekennzeichnet, daß in diesen Elektroden außer der regulären, bisher für alkalische Elemente normalerweise verwendeten aktiven- Masse noch solche Stoffe, z. B. Cadmiumoxyd, Cadmiumhydroxyd, Eisenhydroxyd usw. bzw. Nickel-(2)-Hydroxyd, Kupferpulver usw.,. in ausreichender Menge vorhanden sind, die nach erfolgter erschöpfender Entladung der regulären Masse einer elektrochemischen Reduktion (Oxydation) unterliegen. und dadurch die sonst unmittelbar nach der Umpolungeintretende Wasserstoff- bzw. Sauerstoffentwicklung unterdrücken. i. Positive or negative electrodes for alkaline batteries, which are used with further over their polarity reversal does not develop hydrogen (oxygen) beyond the flowing discharge voltage, characterized in that in these electrodes except for the regular, so far for alkaline elements normally used active mass nor such substances, e.g. B. cadmium oxide, Cadmium hydroxide, iron hydroxide etc. or nickel (2) hydroxide, copper powder etc.,. are available in sufficient quantities, after the exhaustive discharge of the regular mass of an electrochemical reduction (Oxidation). and thereby that which otherwise occurs immediately after the polarity reversal Suppress the development of hydrogen or oxygen. 2'. Ausführungsform nach Anspruch 1, da-• durch gekennzeichnet, daß die elektrochemisch reduzierbaren bzw. oxydierbaren Stoffe in besonderen Taschen, Röhrchen oder Plattem der Elementelektroden untergebracht sind.2 '. Embodiment according to claim 1, that • characterized in that the electrochemically reducible or oxidizable substances in particular Bags, tubes or plates of the element electrodes are housed. 3. Ausführungsform nach Anspruch 1, dadurch' gekennzeichnet, daß die elektrochemisch reduzierbaren bzw. oxydierbaren Stoffe mit der regulären aktiven Masse mehr oder weniger innig vermischt oder gemeinsam mit ihr aus Lösungen ausgefällt sind.3. Embodiment according to claim 1, characterized ' characterized in that the electrochemically reducible or oxidizable substances with the regular active material more or less intimately mixed or together with her failed solutions. ι 5637 11. S3ι 5637 11th S3
DEA14618A 1951-12-01 1951-12-01 Positive and negative electrodes for alkaline batteries Expired DE899216C (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BE515722D BE515722A (en) 1951-12-01
NL88619D NL88619C (en) 1951-12-01
DEA14618A DE899216C (en) 1951-12-01 1951-12-01 Positive and negative electrodes for alkaline batteries
AT181300D AT181300B (en) 1951-12-01 1952-11-14 Electrodes for alkaline batteries
CH314756D CH314756A (en) 1951-12-01 1952-11-22 Electrode for alkaline batteries
FR1066769D FR1066769A (en) 1951-12-01 1952-11-24 electrodes for accumulators
GB30287/52A GB784851A (en) 1951-12-01 1952-11-28 Improvements in or relating to alkaline electrlc accumulators

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA14618A DE899216C (en) 1951-12-01 1951-12-01 Positive and negative electrodes for alkaline batteries

Publications (1)

Publication Number Publication Date
DE899216C true DE899216C (en) 1953-12-10

Family

ID=6923252

Family Applications (1)

Application Number Title Priority Date Filing Date
DEA14618A Expired DE899216C (en) 1951-12-01 1951-12-01 Positive and negative electrodes for alkaline batteries

Country Status (7)

Country Link
AT (1) AT181300B (en)
BE (1) BE515722A (en)
CH (1) CH314756A (en)
DE (1) DE899216C (en)
FR (1) FR1066769A (en)
GB (1) GB784851A (en)
NL (1) NL88619C (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1082640B (en) * 1957-09-28 1960-06-02 Grubenlampenwerke Veb Process for the production of the positive electrode mass for permanently gas-tight sealed nickel-cadmium accumulators
DE1086311B (en) * 1954-07-14 1960-08-04 Accumulatoren Fabrik Ag Permanently gas- and liquid-tight sealed accumulator with alkaline electrolyte
DE1151291B (en) * 1959-07-22 1963-07-11 Accumulateurs Fixes Alkaline accumulators, counter cells or the like.
DE1173155B (en) * 1958-10-08 1964-07-02 Varta Ag Permanently gas-tight sealed alkaline accumulator cell and process for their production
DE1175302B (en) * 1957-12-21 1964-08-06 Varta Ag Permanently gas- and liquid-tight sealed alkaline accumulator
DE1175303B (en) * 1958-01-25 1964-08-06 Varta Ag Alkaline accumulator in which the development of hydrogen is prevented when oxygen is consumed
DE1195833B (en) * 1960-10-21 1965-07-01 Svenska Ackumulator Ab Gas-tight sealed, alkaline accumulator and process for its production
DE2445096A1 (en) * 1974-06-17 1975-12-18 Gen Electric RECHARGEABLE CELL

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1086311B (en) * 1954-07-14 1960-08-04 Accumulatoren Fabrik Ag Permanently gas- and liquid-tight sealed accumulator with alkaline electrolyte
DE1082640B (en) * 1957-09-28 1960-06-02 Grubenlampenwerke Veb Process for the production of the positive electrode mass for permanently gas-tight sealed nickel-cadmium accumulators
DE1175302B (en) * 1957-12-21 1964-08-06 Varta Ag Permanently gas- and liquid-tight sealed alkaline accumulator
DE1175303B (en) * 1958-01-25 1964-08-06 Varta Ag Alkaline accumulator in which the development of hydrogen is prevented when oxygen is consumed
DE1173155B (en) * 1958-10-08 1964-07-02 Varta Ag Permanently gas-tight sealed alkaline accumulator cell and process for their production
DE1151291B (en) * 1959-07-22 1963-07-11 Accumulateurs Fixes Alkaline accumulators, counter cells or the like.
DE1195833B (en) * 1960-10-21 1965-07-01 Svenska Ackumulator Ab Gas-tight sealed, alkaline accumulator and process for its production
DE2445096A1 (en) * 1974-06-17 1975-12-18 Gen Electric RECHARGEABLE CELL

Also Published As

Publication number Publication date
GB784851A (en) 1957-10-16
NL88619C (en)
BE515722A (en)
AT181300B (en) 1955-03-10
CH314756A (en) 1956-06-30
FR1066769A (en) 1954-06-09

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