DE929560C - Galvanic element - Google Patents

Galvanic element

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Publication number
DE929560C
DE929560C DEP22110A DEP0022110A DE929560C DE 929560 C DE929560 C DE 929560C DE P22110 A DEP22110 A DE P22110A DE P0022110 A DEP0022110 A DE P0022110A DE 929560 C DE929560 C DE 929560C
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Prior art keywords
amalgam
alkali
electrode
sodium
galvanic element
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Expired
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DEP22110A
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German (de)
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Helmut Jedlicka
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Individual
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Individual
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Priority claimed from GB20388/48A external-priority patent/GB640496A/en
Application filed by Individual filed Critical Individual
Priority to DEP22110A priority Critical patent/DE929560C/en
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Publication of DE929560C publication Critical patent/DE929560C/en
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    • 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
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/30—Deferred-action cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/30—Deferred-action cells
    • H01M6/32—Deferred-action cells activated through external addition of electrolyte or of electrolyte components
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

(WiGBl. S. 175)(WiGBl. P. 175)

AUSGEGEBEN AM 30. JUNI 1955ISSUED JUNE 30, 1955

ρ 221 ίο IV b j2i bDρ 221 ίο IV b j2i bD

Galvanisches ElementGalvanic element

Die Erfindung betrifft ein galvanisches Element mit einer Alkalilauge als Elektrolyt und einer positiven Elektrode, die ans einem im Elektrolyten ! praktisch unlöslichen Metalloxyd, wie CuO, Ag2O, Xi O.„ oder aus Kohle besteht. Gemäß der Erfindung besteht die negative Elektrode aus flüssigem Alkali-Metall-Amalgam. Die bisher bekanntgewordenen Versuche, in galvanischen Elementen die Oxydation der Alkalimetalle in der Weise auszunutzen, daß diesen Elementen praktisch brauchbare Ströme, /.. ß. für ßeleuchtungszwecke. Rundfunkempfänger, Fernsprechanlagen, entnommen werden können, sind, soweit bekannt, ohne wesentlichen Erfolg geblieben. Es sind in der Literatur Elemente mit fester Xatrium- Amalgam -Elektrode beschrieben worden, eine Ausführung, die nach den Erkenntnissen des Erfinders wegen der zu großen Zersetzuiigsgeschwindigkeit des Amalgams unbrauchbar ist. Bei einem anderen Element soll die Quecksilberelektrode laufend mittels eines eintauchenden Stabes aus metallisch reinem Xatrium aktiviert werden. Bei dieser Anordnung muß aber die Ingangsetzung des Elements weitgehend dem Zufall überlassen werden, und es bildet sich an der Eintauchstelle des Xatriumstabes ein fester Amalgamklumpen, so daß die Beherrschung der Amalgamkonzentration im wirksamen Teil der Elektrode ausgeschlossen ist.The invention relates to a galvanic element with an alkali as the electrolyte and a positive electrode that is in the electrolyte! practically insoluble metal oxide, such as CuO, Ag 2 O, Xi O. "or carbon. According to the invention, the negative electrode consists of liquid alkali metal amalgam. The previously known attempts to exploit the oxidation of the alkali metals in galvanic elements in such a way that these elements have practically usable currents, / .. ß. for lighting purposes. Radio receivers, telephone systems, have, as far as is known, remained without significant success. Elements with a solid sodium amalgam electrode have been described in the literature, a design which, according to the inventor's knowledge, is unusable because of the excessive rate of decomposition of the amalgam. In the case of another element, the mercury electrode is to be activated continuously by means of an immersed rod made of metallically pure sodium. With this arrangement, however, the activation of the element must largely be left to chance, and a solid lump of amalgam forms at the point where the sodium rod is immersed, so that it is impossible to control the amalgam concentration in the active part of the electrode.

Der Erfinder hat festgestellt (vgl. Z. Natu-rforschg. 3 a, 670 und 671 [1948], und 4a, 301 und 302 [1949]), daß das galvanische Element Xa-Amalgam-'XaOH/CuO zu praktisch brauchbarer stromliefernder Arbeit überhaupt nur dann fähig ist, wenn die Konzentration der Alkali-Amalgam-Elektrode unter 3 Gewichtsprozent Alkalimetall liegt.The inventor has established (see Z. Natu-rforschg. 3 a, 670 and 671 [1948], and 4a, 301 and 302 [1949]) that the galvanic element Xa-Amalgam-'XaOH / CuO only then capable of practically useful electricity-supplying work is when the concentration of the alkali amalgam electrode is below 3 percent by weight alkali metal lies.

Die besten Ergebnisse wurden mit Konzentrationen unter 0,8 Gewichtsprozent, vorzugsweise mit etwa 0,5 Gewichtsprozent erzielt.The best results have been obtained with concentrations below 0.8 percent by weight, preferably with about 0.5 percent by weight achieved.

Beispielsweise kann die positive Elektrode aus Silberoxyd, der Elektrolyt aus Natronlauge der ungefähren Dichte 1,2 und die Amalgamelektrode aus einer flüssigen Elektrode mit' einem Gehalt von 0,5 Gewichtsprozent Natrium (0,5 g Na zu 99,5 g Hg) bestehen. Ein solches Element liefert, wie der Versuch gezeigt hat, eine elektromotorische Kraft von etwa 2,4 Volt. In gleicher Anordnung liefert eine Kupferoxydelektrode etwa 1,6 Volt und Kohle etwa 1,9 Volt. Die Amalgamelektrode ist dabei bis zu etwa 0,1 A/cm2 Oberfläche belastbar. Der Ah-Nutzeffekt in bezug auf den Natriumverbrauch erreicht 80 bis 90% des theoretischen Wertes (23 g Na soll 26,8Ah)1 so daß aus 1 g Natrium rund ι Amperestunde elektrische Energie erzielt wird. Die Elemente sind reversibel, also auch als Sekundärelemente verwendbar.For example, the positive electrode can consist of silver oxide, the electrolyte of sodium hydroxide solution with an approximate density of 1.2 and the amalgam electrode of a liquid electrode with a sodium content of 0.5 percent by weight (0.5 g Na to 99.5 g Hg). As the experiment has shown, such an element delivers an electromotive force of about 2.4 volts. In the same arrangement, a copper oxide electrode supplies about 1.6 volts and carbon about 1.9 volts. The amalgam electrode can be loaded up to about 0.1 A / cm 2 surface. The Ah efficiency in relation to sodium consumption reaches 80 to 90% of the theoretical value (23 g Na should be 26.8 Ah) 1 so that around 1 ampere hour of electrical energy is obtained from 1 g of sodium. The elements are reversible, so they can also be used as secondary elements.

Sehr brauchbare Primärelemente werden mit Gegenelektroden aus Kohle und ebenso aus Kupferoxyd erzielt. Beim System Kohie/Alkalilauge/Alkali-Amalgatn wird der Luftsauerstoff wie bei den bekannten LuftsauerstofFelementen des Leclanchetyps zur Depolarisation benutzt. Beim System Kupferoxyd/Alkalilauge/Alkali - Amalgam dient gewissermaßen ebenfalls der Luftsauerstoff als Depolarisator, da sich bekanntlich bei stromliefernder Arbeit das Kupferoxyd in Kupferoxydul Cu2O bzw. in Kupfer verwandelt, welches sich an warmer Luft leicht in Kupferoxyd aufoxydieren läßt. Elemente gemäß der Erfindung Hefern dauernd eine konstante Spannung, sofern dafür gesorgt wird, daß die Amalgam- und Laugenkonzentration im wesentlichen konstant bleibt. Durch laufende Zugaben von metallischem Natrium oder Kalium oder einer evtl. flüssigen Legierung beider, die ohne Berührung mit dem Elektrolyten, z. B. durch ein Rohr, direkt in das Quecksilber einzuführen sind, gelingt leicht die Aufrechterhaltung der Arnalgamkonzentration in den erforderlichen Grenzen. Durch teilweisen Abfluß von Lauge und Wasserzufluß ist die Laugenkonzentration in ihren Grenzen zu halten.Very useful primary elements are achieved with counter electrodes made of carbon and also of copper oxide. In the Kohie / alkali lye / alkali amalgate system, the oxygen in the air is used for depolarization, as is the case with the known air oxygen elements of the Leclanche type. In the system copper oxide / alkali lye / alkali - amalgam, the oxygen in the air also serves as a depolarizer, as it is known that during work that supplies electricity, the copper oxide is transformed into copper oxide Cu 2 O or into copper, which can easily be oxidized into copper oxide in warm air. Elements according to the invention yeasts maintain a constant voltage at all times, provided that it is ensured that the amalgam and alkali concentration remains essentially constant. With continuous additions of metallic sodium or potassium or a possibly liquid alloy of both, which do not come into contact with the electrolyte, e.g. B. through a pipe to be introduced directly into the mercury, it is easy to maintain the arnalgam concentration within the required limits. The alkali concentration must be kept within its limits by partial drainage of the alkali and water inflow.

Ein anderer Weg zur Aufrechterhaltung der Amalgamkonzentration besteht in der Verwendung eines von der eigentlichen Zelle getrennten Raumes, der Amalgamierungskammer. Diese enthält Ouecksilber, dem z. B. Natrium irgendwie zugeführt wird, worauf das Amalgam mittels Umlauf durch die Zelle geführt wird, dort sein Natrium bei stromliefernder Arbeit abgibt, um in der Amalgamierungskammer erneut mit Natrium beladen zu werden. Für diesen Umlauf empfiehlt sich ein sehr flüssiges Amalgam mit einem Na-Gehalt unter 0,8%, vorteilhaft mit etwa 0,5 Gewichtsprozent.Another way to maintain amalgam concentration is by use a room separate from the actual cell, the amalgamation chamber. This contains silver, the z. B. sodium is somehow supplied, whereupon the amalgam by means of circulation the cell is led, there its sodium gives off during current-supplying work to the amalgamation chamber to be reloaded with sodium. A very liquid amalgam with an Na content below is recommended for this circulation 0.8%, advantageously with about 0.5% by weight.

Kleinbatterien für Beleuchtungszwecke, für Radio, Telefon u. dgl., werden mit Erfolg z. B. so ausgebildet, daß ihre Kupferoxydelektrode bei Nichtbenutzung durch Kippen oder Herausheben aus dem Elektrolyten mit Luft in Berührung kommt und dadurch regeneriert wird. Für sie empfiehlt sich, die jeweilige Aktivierung der negativen Quecksilberelektrode durch Zufügen von festem Na-Amalgarn, vorteilhaft mit einem Natriumgehalt von 23 Gewichtsprozent vorzunehmen. Dieses sehr harte und einheitliche Amalgam eignet sich z. B. zur Herstellung kleiner Schrotkugeln, die aus einer kleinen Kammer, unter Petroleum gehalten, nach Belieben durch den Elektrolyten in die am Boden des Elementes angeordnete Ouecksilberschicht fallen gelassen werden können, wo sie sich schnellstens verteilen und bei Berührung mit der Hg-Oberfläche augenblicklich die Stromlieferung der Zelle veranlassen. Selbst sehr kleine Zellen Cu O/Na O H/Hg-Na liefern bei einer Belastung von etwa 0,1 A/cm2 Hg-Oberfläche eine konstante Spannung von etwa 1,3 Volt, so daß nach Einwerfen von nur 1 g 23°/oigem Natriumamalgam rund 0,3 Wattstunden elektrische Leistung dem Element entnommen werden kann.Small batteries for lighting purposes, for radio, telephone and the like., Are successfully z. B. designed so that its copper oxide electrode comes into contact with air when not in use by tilting or lifting it out of the electrolyte and is thereby regenerated. It is advisable for them to activate the respective negative mercury electrode by adding solid Na amal yarn, advantageously with a sodium content of 23 percent by weight. This very hard and uniform amalgam is suitable for B. for the production of small shotgun pellets, which from a small chamber, kept under petroleum, can be dropped at will through the electrolyte into the ouck silver layer arranged at the bottom of the element, where they are distributed as quickly as possible and instantly when they come into contact with the Hg surface Arrange for the cell to be supplied with electricity. Even very small cells Cu O / Na OH / Hg-Na deliver a constant voltage of about 1.3 volts at a load of about 0.1 A / cm 2 Hg surface, so that after throwing in only 1 g 23 ° / oigem sodium amalgam around 0.3 watt hours of electrical power can be drawn from the element.

Die Kupferoxydelektrode ist in bekannter Weise, wie auch beim Element CuO/NaOH/Zn herstellbar. In der einfachsten Form wird CuO, z. B. Granulat, in einen Kupferdrahtnetzbeutel eingefüllt. Die Herstellung des 23°/«gen Amalgams geschieht durch Erwärmen einer Ouecksilbermenge unter Petroleum auf etwa 100'- C, worauf die erforderliche Menge Natrium (zu 1J1J Teilen Quecksilber 23 Teile metall. Natrium] in kleinen Portionen zugefügt wird.The copper oxide electrode can be produced in a known manner, as is the case with the element CuO / NaOH / Zn. In its simplest form, CuO, e.g. B. granules, filled into a copper wire mesh bag. The 23% amalgam is produced by heating an amount of mercury under petroleum to about 100 ° C., whereupon the required amount of sodium ( 23 parts of metal sodium to 1 J 1 J parts of mercury) is added in small portions.

Claims (3)

Patentansprüche:Patent claims: 1. Galvanisches Element mit einer Alkalilauge als Elektrolyt und einer positiven Elektrode, bestehend aus einem im Elektrolyten praktisch unlöslichen Metalloxyd, wie CuO, Ag2O, NiO2, oder aus Kohle, und einer negativen Alkali-Amalgam-Elektrode, dadurch gekennzeichnet, daß diese aus flüssigem Alkali-Amalgam besteht. 1. Galvanic element with an alkali as the electrolyte and a positive electrode, consisting of a metal oxide which is practically insoluble in the electrolyte, such as CuO, Ag 2 O, NiO 2 , or of carbon, and a negative alkali amalgam electrode, characterized in that this consists of liquid alkali amalgam. 2. Galvanisches Element nach Anspruch 1, dadurch gekennzeichnet, daß der Alkali-Metall-Gehalt der Alkali-Amalgam-Elektrode weniger als 0,8, vorzugsweise etwa 0,5 Gewichtsprozent beträgt.2. Galvanic element according to claim 1, characterized in that the alkali metal content of the alkali amalgam electrode less than 0.8, preferably about 0.5 percent by weight amounts to. 3. Galvanisches Element nach Anspruch ί oder 2, dadurch gekennzeichnet, daß das verbrauchte Alkalimetall durch Eintragen von Alkali-Amalgam, vorzugsweise in fester Form.3. Galvanic element according to claim ί or 2, characterized in that the consumed Alkali metal by adding alkali amalgam, preferably in solid form. in das verarmte Amalgam ergänzt wird.is replenished in the impoverished amalgam. Angezogene Druckschriften:Referred publications: Deutsche Patentschrift Nr. 23 906; L'SA.-Patentschrift Nr, 1 015 734;German Patent No. 23,906; L'SA Patent No. 1,015,734; Drucker-Finkelstein, Galvanische Elemente und Akkumulatoren, 1932, S. 8;Drucker-Finkelstein, Galvanic elements and accumulators, 1932, p. 8; Hansen, Der Aufbau der Zwei-Stoff-Legierungen, 1936, S. 792.Hansen, The Structure of Two-Material Alloys, 1936, p. 792. © 509 520 6.55© 509 520 6.55
DEP22110A 1948-07-30 1948-11-19 Galvanic element Expired DE929560C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEP22110A DE929560C (en) 1948-07-30 1948-11-19 Galvanic element

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB20388/48A GB640496A (en) 1948-07-30 1948-07-30 Improvements in or relating to galvanic cells
DEP22110A DE929560C (en) 1948-07-30 1948-11-19 Galvanic element

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1023500B (en) * 1956-02-24 1958-01-30 Bosch Gmbh Robert Rechargeable primary element
DE1081528B (en) * 1955-07-04 1960-05-12 Accumulatorenfabriek Iavartaia Partly rechargeable galvanic element with alkaline electrolyte
DE1279153B (en) * 1963-01-16 1968-10-03 Mallory Batteries Ltd Rechargeable galvanic element with a negative electrode made of amalgamated zinc

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE23906C (en) * DR. A. BERNSTEIN in Berlin Innovation in galvanic elements
US1015734A (en) * 1910-09-10 1912-01-23 Roessler & Hasslacher Chemical Primary battery.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE23906C (en) * DR. A. BERNSTEIN in Berlin Innovation in galvanic elements
US1015734A (en) * 1910-09-10 1912-01-23 Roessler & Hasslacher Chemical Primary battery.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1081528B (en) * 1955-07-04 1960-05-12 Accumulatorenfabriek Iavartaia Partly rechargeable galvanic element with alkaline electrolyte
DE1023500B (en) * 1956-02-24 1958-01-30 Bosch Gmbh Robert Rechargeable primary element
DE1279153B (en) * 1963-01-16 1968-10-03 Mallory Batteries Ltd Rechargeable galvanic element with a negative electrode made of amalgamated zinc

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